Fluorinated fluorene derivatives

ABSTRACT

The invention relates to fluorinated fluorene derivatives of negative DC anisotropy, of the formula I
 
R 1 —(—A 1 —Z 1 —) k1 —(—A 2 —Z 2 —) k2 —W—(—Z 3 —A 3 —) k3 —(—Z 4 —A 4 —) k4 —R 2 I
 
in which
         W denotes the sub-formula       

     
       
         
         
             
             
         
       
         
         
           
             L 1  and L 2 , independently of one another, are H, F, Cl, —CH 2 F, —CHF 2  or —CF 3 , with the proviso that L 1  and L 2  are not both H, 
             L 3  and L 4 , independently of one another, are H or F, and 
             R 1 , R 2 , A 1 , A 2 , A 3 , A 4 , Z 1 , Z 2 , Z 3 , Z 4 , k1, k2, k3 and k4 are as defined above. The invention furthermore relates to liquid-crystalline media and to optical and electro-optical display elements.

The invention relates to fluorinated fluorene derivatives of the formulaI which have negative anisotropy of the dielectric constants (DCanisotropy),R¹—(—A¹—Z¹—)_(k1)—(—A²—Z²—)_(k2)—W—(—Z³—A³—)_(k3)—(—Z⁴—A⁴—)_(k4)—R²  Iin which

-   -   W is the

-   -    group,    -   L¹ and L², independently of one another, are H, F, Cl, —CH₂F,        —CHF₂ or —CF₃, with the proviso that L¹ and L² are not both H,    -   L³ and L⁴, independently of one another, are H or F,    -   R¹ and R², independently of one another, are H, halogen, —CN,        —NCS, —SF₅ or alkyl having from 1 to 18 carbon atoms, in which,        in addition, one or two non-adjacent —CH₂— groups may be        replaced by —O—, —S—, —CO—, —O—CO—, —CO—O—, —E— and/or —C≡C—        and/or in which, in addition, one or more H atoms may be        replaced by halogen and/or —CN,    -   E is CR⁴═CR⁵ or CHR⁴—CHR⁵,    -   R⁴ and R⁵ are each, independently of one another, H, alkyl        having 1–6 carbon atoms, F, Cl, CF₃ or CN,    -   A¹, A², A³ and A⁴ are each, independently of one another,        1,4-phenylene, in which one or more CH groups may be replaced by        N, 1,4-cyclohexylene, in which one or two non-adjacent CH₂        groups may be replaced by O and/or S, 1,4-cyclohexenylene,        1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl,        naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or        1,2,3,4-tetrahydronaphthalene-2,6-diyl, where, in the meanings        given for A¹, A², A³ and A⁴, one or more H atoms may be        substituted by halogen, —CN and/or alkyl having from 1 to 6        carbon atoms, in which one or more H atoms may be replaced by        halogen or —CN, and/or in which one or more non-adjacent —CH₂—        groups may be replaced, independently of one another, by —CO—,        —O—CO—, —CO—O—, —O—, —S—, —CH═CH— or —C≡C—, and    -   Z¹, Z², Z³ and Z⁴, independently of one another, are —O—CO—,        —CO—O—, —CH₂—O—, —CF₂—O—, —O—CH₂—, —O—CF₂—, —C₂H₄—, —CH₂—CF₂—,        —CF₂—CH₂—, —CF₂—CF₂—, —CH═CH—, —CF═CH—, —CH═CF—, —CF═CF—, —C≡C—        or a single bond,    -   k1, k2, k3 and k4, independently of one another, are 0, 1 or 2.

The invention furthermore relates to liquid-crystalline media whichcomprise the liquid-crystalline media according to the invention and toliquid-crystal and electro-optical display elements which contain theliquid-crystalline media according to the invention.

Fluorinated fluorene derivatives which contain the

group in which X is F or H are described in DE 197 20 289 as componentsof ferroelectric liquid-crystal mixtures. It is stated in this respectthat more negative values of the dielectric anisotropy (Δε) can beobtained by admixing compounds of this type. Use in FLC mixtures foroperation in inverse mode is cited as preferred. However, values forindividual substances or mixtures are not given.

There continues to be a great demand for compounds and media havinghighly to very highly negative dielectric anisotropy Δε, in particularfor those having very high specific resistance at the same time as abroad mesophase range and low viscosity.

The object of the present-invention is to provide novel, stable,liquid-crystalline or mesogenic compounds having highly to very highlynegative DC anisotropy which are suitable as components ofliquid-crystalline media.

The invention furthermore relates to the provision of liquid-crystallinemedia and optical and electro-optical display elements.

The first-mentioned object is achieved by means of fluorene derivativesof the formula I. It has been found that the compounds according to theinvention are eminently suitable as components of liquid-crystallinemedia. They can be used to obtain stable liquid-crystalline media whichare particularly suitable for electro-optical LC displays. The fluorenederivatives according to the invention have highly to very highlynegative Δε values. In general, these values are significantly lowerthan the Δε values of comparable compounds which carry exclusively Hatoms in the 1- and 8-position of the fluorene group. In addition, thefluorene derivatives according to the invention have relatively lowvalues of the optical anisotropy Δn and mesophase ranges which arefavourable for use in electro-optical display elements. Furthermore,these compounds are also stable chemically, thermally and to the actionof light and are readily miscible with other liquid-crystallinesubstances.

The provision of the fluorene derivatives according to the inventionvery generally considerably broadens the range of liquid-crystallinesubstances which are suitable, from various applicational points ofview, for the preparation of liquid-crystalline mixtures.

In addition, the invention relates to a liquid-crystalline medium havingtwo or more liquid-crystalline components, where the medium has at leastone fluorene derivative according to the invention. The use of fluorenederivatives according to the invention enables the dielectric anisotropyof media of this type to be influenced in a targeted manner towardsnegative Δε values, with low viscosities advantageously being achieved.In addition, however, it is also possible to add one or more compoundsaccording to the invention to liquid-crystalline media in order tomodify the optical anisotropy and/or the mesophase ranges and/or thetilt angle of media of this type in a targeted manner.

The compounds according to the invention can be used as components ofliquid-crystalline media, in particular for displays based on theprinciple of the twisted cell, the guest-host effect, the DAP(deformation of aligned phases), ECB (electrically controlledbirefringence), CSH (colour super homeotropic), VA (vertically aligned)or IPS (in-plane switching) effect or the effect of dynamic scattering.

Furthermore, the compounds according to the invention can be used ascomponents of optically active, tilted, smectic (ferroelectric)liquid-crystalline media, in particular for displays based on the SSFLCD(surface stabilised ferroelectric liquid crystal display) effect ofClark and Lagerwall, but also on the DHF (distorted helix formation)effect or the PSFLCD (pitch stabilised ferroelectric liquid crystaldisplay) effect, which is also known as the SBF (short pitch bistableferroelectric) effect.

The invention furthermore relates to an optical display element whichcontains a liquid-crystalline medium according to the invention, and toan electro-optical display element which contains a liquid-crystallinemedium according to the invention as dielectric. The above-mentioneddisplay elements are preferred here.

Above and below, the groups, substituents and indices W, R¹, R², E, R⁴,R⁵, L¹, L², L³, L⁴, Z¹, Z², Z³, Z⁴, A¹, A², A³, A⁴, k1, k2, k3 and k4are as defined in respect of the formula I, unless expressly statedotherwise. If a radical occurs more than once, it may adopt identical ordifferent meanings.

The meaning of the formula I includes all isotopes of the chemicalelements bonded in the compounds of the formula I. In enantiomericallypure or enriched form, the compounds of the formula I are also suitableas chiral dopants and in general for achieving chiral mesophases.

Preferred meanings of groups and substituents of the fluorenederivatives according to the invention are indicated below.

Preferred meanings of the group W are represented by the sub-formulae W1to W3:

Particularly preferred meanings of the sub-formula W1 are represented bythe sub-formulae W11 to W18:

Above and below, I=0, 1 or 2, and consequently the —CH_(I)F_(3−I) groupis —CH₂F, —CHF₂ or —CF₃. I preferably has the value 0 or 1, particularlypreferably the value I=0. If the index I occurs more than once in aformula, this may have identical or different meanings.

Particularly preferred meanings of the sub-formula W2 are represented bythe sub-formulae W21 to W28:

The sub-formula W2 and the corresponding sub-formulae W21 to W28include, in the case where the carbon atom of the

group is a chiral centre, both the racemates and the enantiomericallypure or enriched forms.

Particularly preferred meanings of the sub-formula W3 are represented bythe sub-formulae W31 to W38:

Of the above-mentioned sub-formulae, W1, in particular W11 to W18, andW3, in particular W31 to W38, are very particularly preferred.

According to a first preferred embodiment of the invention, k1, k2, k3and k4 have the value 0, and the compounds according to the inventiontherefore have the formula IaR¹—W—R²  Ia.

At least one of the groups R¹ or R² here, preferably R¹ and R², has,independently of one another, the meaning alkyl having from 1 to 18carbon atoms, in which, in addition, one or two non-adjacent —CH₂—groups and/or in addition one or more H atoms may be replaced asindicated.

Particular preference is given to compounds of the sub-formulae Ia1 toIa10R¹-W11-R²  Ia1R¹-W13-R²  Ia2R¹-W14-R²  Ia3R¹-W16-R²  Ia4R¹-W18-R²  Ia5R¹-W31-R²  Ia6R¹-W33-R²  Ia7R¹-W34-R²  Ia8R¹-W36-R²  Ia9R¹-W38-R²  Ia10with the meanings indicated above for W11 to W38.

According to a second preferred embodiment, at least one of the indicesk1, k2, k3 and/or k4 has a value not equal to zero.

According to a preferred first variant in this respect, k1=1 andk2=k3=k4=0, so that the fluorene derivatives have the formula IbR¹—A¹—Z¹—W—R²  Ib.

According to a preferred second variant, k1=k2=1 and k3=k4=0, so thatthe fluorene derivatives have the formula IcR¹—A¹—Z¹—A²—Z²—W—R²  Ic.

According to a preferred third variant, k1=k3=1 and k2=k4=0, so that thefluorene derivatives have the formula IdR¹—A¹—Z¹—W—Z³—A³—R²  Id.

Particularly preferred meanings of A¹, A², A³ and/or A⁴ are,independently of one another, 1,4-phenylene, which may bemonosubstituted, disubstituted or trisubstituted by fluorine,trans-1,4-cyclohexylene and 1,3-dioxane-2,5-diyl, for which, for reasonsof simplicity, the abbreviations Phe, Cyc and Dio respectively are usedbelow.

The term 1,3-dioxane-2,5-diyl in each case covers the two positionalisomers

If, in accordance with the second embodiment, the compounds contain asix-membered ring in addition to the group W, the following compounds ofthe sub-formulae Ib1 to Ib3 are preferred:R¹-Cyc-Z¹—W—R²  Ib1R¹-Phe-Z¹—W—R²  Ib2R¹-Dio-Z¹—W—R²  Ib3

If, in accordance with the second embodiment, the compounds contain twosix-membered rings in addition to the group W, the following compoundsof the sub-formulae Ic1 to Ic9 and Id1 to Id9 are preferred:R¹-Cyc-Z¹-Cyc-Z²—W—R²  Ic1R¹-Cyc-Z¹-Phe-Z²—W—R²  Ic2R¹-Cyc-Z¹-Dio-Z²—W—R²  Ic3R¹-Phe-Z¹-Cyc-Z²—W—R²  Ic4R¹-Phe-Z¹-Phe-Z²—W—R²  Ic5R¹-Phe-Z¹-Dio-Z²—W—R²  Ic6R¹-Dio-Z¹-Cyc-Z²—W—R²  Ic7R¹-Dio-Z¹-Phe-Z²—W—R²  Ic8R¹-Dio-Z¹-Dio-Z²—W—R²  Ic9R¹-Cyc-Z¹—W—Z³-Cyc-R²  Id1R¹-Cyc-Z¹—W—Z³-Phe-R²  Id2R¹-Cyc-Z¹—W—Z³-Dio-R²  Id3R¹-Phe-Z¹—W—Z³-Cyc-R²  Id4R¹-Phe-Z¹—W—Z³-Phe-R²  Id5R¹-Phe-Z¹—W—Z³-Dio-R²  Id6R¹-Dio-Z¹—W—Z³-Cyc-R²  Id7R¹-Dio-Z¹—W—Z³-Phe-R²  Id8R¹-Dio-Z¹—W—Z³-Dio-R²  Id9

The compounds in accordance with the second embodiment may also containthree or more six-membered rings in addition to the group W.

If L³ and L⁴ are H, preference is given to the fluorene derivatives ofthe formula I in which R¹—(—A¹—Z¹—)_(k1)—(—A²—Z²—)k₂— and—(—Z³—A³—)_(k3)—(—Z⁴—A⁴—)k₄—R² are selected in such a way that thefluorene derivative has a dielectric anisotropy Δε of less than or equalto −2.0, particularly preferably less than or equal to −4.0, veryparticularly preferably less than or equal to −5.0.

If L³ or L⁴ is F and the other substituent L⁴ or L³ is H, preference isgiven to the fluorene derivatives of the formula I in whichR¹—(—A¹—Z¹—)_(k1)—(—A²—Z²—)k₂— and —(—Z³—A³—)_(k3)—(—Z⁴—A⁴—)_(k4)—R² areselected in such a way that the fluorene derivative has a dielectricanisotropy Δε of less than or equal to −6.0, particularly preferablyless than or equal to −8.0, very particularly preferably less than orequal to −10.0.

If L³ and L⁴ are F, preference is given to the fluorene derivatives ofthe formula I in which R¹—(—A¹—Z¹—)_(k1)—(—A²—Z²—)_(k2)— and—(—Z³—A³—)_(k3)—(—Z⁴—A⁴—)_(k4)—R² are selected in such a way that thefluorene derivative has a dielectric anisotropy Δε of less than or equalto −8.0, in particular less than or equal to −10.0, particularlypreferably less than or equal to −12.0, very particularly preferablyless than or equal to −15.0.

In the case of the meaning alkyl in the groups or substituents indicatedabove or below, in particular in R¹ and/or R²,the alkyl radical may belinear or branched. It preferably has 1, 2, 3, 4, 5, 6, 7 or 8 carbonatoms. It is preferably linear and is therefore particularly methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl.

R¹ and/or R² are preferably alkyl, alkenyl, alkoxy, alkenyloxy,oxaalkyl, oxaalkenyl, alkylcarbonyloxy or alkyloxycarbonyl.

Besides the above-mentioned meanings in the case of alkyl, R¹ and R² asalkyl may also have more than 8 carbon atoms and are thereforeparticularly nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl orpentadecyl.

Further preferred meanings of R¹ and/or R² are alkoxy. The alkoxyradical may be linear or branched. It is preferably linear and has 1, 2,3, 4, 5, 6, 7 or 8 carbon atoms and is therefore particularly methoxy,ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, furthermorenonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

Furthermore, R¹ and/or R² are preferably oxaalkyl. The radical may belinear or branched. It is preferably linear and is, for example,2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl(=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-,3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-,5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7- 8- or 9-oxadecyl.

If R¹ and/or R² are an alkenyl radical, this may be straight-chain orbranched. It is preferably straight-chain and has from 2 to 8 carbonatoms. Accordingly, it is in particular vinyl, prop-1- or -2-enyl,but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or 4-enyl, hex-1-, -2-, -3-,-4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl or oct-1-, -2-,-3-, -4-, -5-, -6- or -7-enyl.

If R¹ and/or R² is an alkenyloxy radical, this may be straight-chain orbranched. It is preferably straight-chain and accordingly is inparticular vinyloxy, prop-1- or -2-enyloxy, but-1-, -2- or -3-enyloxy,pent-1-, -2-, -3- or -4-enyloxy, hex-1-, -2-, -3-, -4- or -5-enyloxy,hept-1-, -2-, -3-, -4-, -5- or -6-enyloxy or oct-1-, -2-, -3-, -4-, -5-,-6- or -7-enyloxy.

If R¹ and/or R² are an oxaalkenyl radical, this may be straight-chain orbranched. It is preferably straight-chain and is particularly preferably3-oxabut-1-enyl (=methoxyvinyl), 2-oxabut-3-enyl (=vinyloxymethyl),4-oxapent-1-enyl (=methoxyprop-1-enyl), 3-oxapent-1-enyl (=ethoxyvinyl),4-oxapent-2-enyl (=methoxyprop-2-enyl), 2-oxapent-3-enyl(=prop-1-enoxymethyl), 2-oxapent-4-enyl (=prop-2-enoxymethyl),3-oxapent-4-enyl (=vinyloxyethyl), 3-oxahex-1-enyl, 4-oxahex-1-enyl,5-oxahex-1-enyl, 4-oxahex-2-enyl, 5-oxahex-2-enyl, 2-oxahex-3-enyl,5-oxahex-3-enyl, 2-oxahex-4-enyl, 3-oxahex-4-enyl, 2-oxahex-5-enyl,3-oxahex-5-enyl or 4-oxahex-5-enyl.

If R¹ and/or R² are an alkyl radical in which one CH₂ group has beenreplaced by —O— and one has been replaced by —CO—, these are preferablyadjacent. This thus contains a carbonyloxy group (acyloxy group) —CO—O—or an oxycarbonyl group —O—CO—. These are preferably straight-chain andhave from 2 to 6 carbon atoms. Accordingly, they are in particularacetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy,acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl,2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetoxypropyl,3-propionyloxypropyl, 4-acetoxybutyl, methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl,ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl,2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl,2-(propoxycarbonyl)-ethyl, 3-(methoxycarbonyl)propyl,3-(ethoxycarbonyl)propyl or 4-(methoxycarbonyl)butyl.

Compounds of the formula I having a branched wing group R¹ and/or R² mayoccasionally be of importance owing to better solubility in theconventional liquid-crystalline base materials, but in particular aschiral dopants if they are optically active. Smectic compounds of thistype are particularly suitable as components of ferroelectric materials.

Branched groups of this type generally contain not more than one chainbranch. Preferred chiral branched radicals R¹ and/or R² are 2-butyl(=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl,2-ethylhexyl, 2-propylpentyl, 2-octyl, in particular 2-methylbutyl,2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy,1-methylhexoxy, 1-methylheptyloxy, 2-octyloxy, 2-oxa-3-methylbutyl,3-oxa-4-methylpentyl, 4-methylhexyl, 2-nonyl, 2-decyl, 2-dodecyl,6-methoxyoctoxy, 6-methyloctoxy, 6-methyloctanoyloxy,5-methylheptyloxycarbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy,4-methylhexanoyloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxahexyl,1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy,1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy.

Preferred achiral branched radicals R¹ and/or R² are isopropyl, isobutyl(=2-methylpropyl), isopentyl (=3-methylbutyl), isopropoxy,2-methylpropoxy and 3-methylbutoxy.

The formula I covers both the racemates of these compounds and theoptical antipodes, and mixtures thereof.

In the case of the above-mentioned meanings of R¹ and R², in particularas alkyl, alkenyl, alkoxy, alkenyloxy, oxaalkyl, oxaalkenyl,alkylcarbonyloxy or alkyloxycarbonyl, one or more H atoms havepreferably been replaced by halogen atoms, preferably by fluorine and/orchlorine, particularly preferably by fluorine. Preferably, 2 or more Hatoms have been substituted by fluorine. Particularly preferably, 2 or 3H atoms in the terminal methyl group in the above-mentioned radicalshave been substituted by fluorine, so that the above-mentioned radicalscontain a —CHF₂ or a —CF₃ group. The entire radical R¹ and/or R² canalso be perfluorinated.

Of the compounds of the formula I and the sub-formulae, preference isgiven to those in which at least one of the radicals present therein hasone of the preferred meanings indicated.

The compounds according to the invention are prepared by methods knownper se from the literature, as described in the standard works onorganic synthesis, for example Houben-Weyl, Methoden der OrganischenChemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart.The preparation is carried out here under reaction conditions which areknown and suitable for the said reactions. Use can also be made here ofsynthetic variants which are known per se, but are not mentioned here ingreater detail. The starting materials and/or intermediates can also, ifnecessary, be formed in situ, i.e. they are not isolated from thereaction mixture, but instead immediately converted further.

The synthesis of three compounds of the formulae Ia-W1, Ia-W2 and Ia-W3according to the invention starting from the fluorenone compound of theformula IIa is indicated by way of example with reference to reactionscheme 1. The formation of the compound Ia-W1 is carried out using asuitable reducing agent, such as, for example, NaBH₄, in the presence ofAlCl₃ and tetrahydrofuran (THF) as solvent.

In the synthesis of compounds of the formula Ia-W2, a reduction iscarried out first, followed by a fluorination, for example using NaBH₄and subsequently diethylaminosulfur trifluoride (DAST). A furtherpossible synthesis proceeds in two steps via a phenyl sulfide. Thecarbonyl compound (here the fluorenone) is firstly reacted withphenylthiol with catalysis by boron trifluoride monohydrate andsubsequently reduced using triethylsilane. In the second step, thephenyl sulfide obtained is fluorinated using nitrosoniumtetrafluoroborate/pyridine/HF complex (Ch. York et al., Tetrahedron 52,1996, 9–14).

In order to prepare the 9,9-difluorofluorenes of the formula Ia-W3,firstly the fluorenone compound of the formula IIa is converted into thecorresponding dithioketal, for example by reaction withethane-1,2-dithiol in the presence of boron trifluoride. The dithioketalis subsequently subjected to oxidative fluorodesulfurisation in thepresence of a fluorinating agent and an oxidant. The oxidant employed ispreferably a compound which liberates halonium equivalents. Illustrativeoxidants are N-bromosuccinimide, N-iodosuccinimide,1,3-dibromo-5,5-dimethylhydantoin and bromine. Also suitable are, forexample, SO₂Cl₂, SO₂ClF, nitrosonium and nitronium salts (C. York inloco citato) and chloramine T. The nitrosonium and nitronium salts canalso, if desired, be prepared in situ from suitable precursors, forexample from inorganic or organic nitrites and/or nitrates. Fluorinatingagents which can be employed are conventional fluorinating agents. Thefluorinating agent is particularly preferably selected from the groupformed by aliphatic and aromatic amine/hydrogen fluoride complexes, suchas, for example, pyridine/hydrogen fluoride complexes, NEt₃.3HF,melamine/HF and polyvinylpyridine/HF.

The reaction conditions to be observed in the said reactions are knownper se to the person skilled in the art. In general, the reaction iscarried out at a temperature of from −100 to +50° C. As solvent, use ismade of inert polar solvents or mixtures thereof, for example ethers orhaloalkanes, such as diethyl ether, tetrahydrofuran or dichloromethane.

A suitable synthetic route for the preparation of the fluorenones of theformula IIa is indicated in reaction scheme 2. According to this, thesynthesis is carried out starting from the brominated aromatic compoundof the formula Va via the corresponding boron compound IVa andcross-coupling thereof with the brominated aromatic compound of theformula Va′ to give the biphenyl compound of the formula IIIa, which isreacted with dimethyl carbonate to give the fluorenone (R. D. Chamber etal., JCS (C) 1968, 2394).

In the reaction schemes 1 and 2, R¹, R², L¹ and L² are as defined above.The syntheses described are suitable not only for compounds of theformula Ia, which have been selected here for reasons of clarity, butalso for all compounds of the formula I according to the invention.

Further suitable possible syntheses can be obtained by the personskilled in the art by analogous use of the syntheses described inreaction schemes 1 to 8 of DE 197 20 289 A1.

Esters of the formula I can also be obtained by esterification ofcorresponding carboxylic acids (or reactive derivatives thereof usingalcohols or phenols (or reactive derivatives thereof or by the DCCmethod (DCC=dicyclohexylcarbodiimide).

The corresponding carboxylic acids and alcohols are known or can beprepared analogously to known processes.

Suitable reactive derivatives of the said carboxylic acids are inparticular the acid halides, especially the chlorides and bromides,furthermore the anhydrides, azides or esters, in particular alkyl estershaving 1–4 carbon atoms in the alkyl group.

Suitable reactive derivatives of the said alcohols are, in particular,the corresponding metal alkoxides, preferably of an alkali metal, suchas Na or K.

The esterification is advantageously carried out in the presence of aninert solvent. Highly suitable solvents are, in particular, ethers, suchas diethyl ether, di-n-butyl ether, THF, dioxane and anisole, ketones,such as acetone, butanone or cyclohexanone, amides, such as DMF orhexamethylphosphoric triamide, hydrocarbons, such as benzene, toluene orxylene, halogenated hydrocarbons, such as tetrachloromethane ortetrachloroethylene, and sulfoxides, such as dimethyl sulfoxide orsulfolane. Water-immiscible solvents may advantageously be used at thesame time for azeotropic removal by distillation of the water formedduring the esterification. An excess of an organic base, for examplepyridine, quinoline or triethylamine, may occasionally also be used assolvent for the esterification. The esterification may also be carriedout in the absence of a solvent, for example by simple heating of thecomponents in the presence of sodium acetate. The reaction temperatureis usually between −50° C. and +250° C., preferably between −20° C. and+80° C. At these temperatures, the esterification reactions aregenerally complete after from 15 minutes to 48 hours.

In detail, the reaction conditions for the esterification dependsubstantially on the nature of the starting materials used. Thus, a freecarboxylic acid is generally reacted with a free alcohol in the presenceof a strong acid, for example a mineral acid, such as hydrochloric acidor sulfuric acid. A preferred reaction procedure is the reaction of anacid anhydride or in particular an acid chloride with an alcohol,preferably in a basic medium, important bases being, in particular,alkali metal hydroxides, such as sodium hydroxide or potassiumhydroxide, alkali metal carbonates or hydrogencarbonates, such as sodiumcarbonate, sodium hydrogencarbonate, potassium carbonate or potassiumhydrogencarbonate, alkali metal acetates, such as sodium acetate orpotassium acetate, alkaline earth metal hydroxides, such as calciumhydroxide, or organic bases, such as triethylamine, pyridine, lutidine,collidine or quinoline. A further preferred embodiment of theesterification comprises firstly converting the alcohol into the sodiumalkoxide or potassium alkoxide, for example by treatment with ethanolicsodium hydroxide solution or potassium hydroxide solution, isolatingthis alkoxide, and reacting it with an acid anhydride or in particularan acid chloride.

In a further process for the preparation of the compounds of the formulaI in which Z¹, Z², Z³ or Z⁴ is —CH═CH—, an aryl halide is reacted withan olefin in the presence of a tertiary amine and in the presence of apalladium catalyst (cf. R. F. Heck, Acc. Chem. Res. 12 (1979) 146).Examples of suitable aryl halides are chlorides, bromides and iodides,in particular bromides and iodides. The tertiary amines necessary forthe success of the coupling reaction, such as, for example,triethylamine, are also suitable as solvent. Examples of suitablepalladium catalysts are the salts thereof, in particular Pd(II) acetate,with organic phosphorus(III) compounds, such as, for example,triarylphosphines. The process can be carried out in the presence orabsence of an inert solvent at temperatures between about 0° C. and 150°C., preferably between 20° C. and 100° C.; suitable solvents are, forexample, nitriles, such as acetonitrile, or hydrocarbons, such asbenzene or toluene. The aryl halides and olefins employed as startingmaterials are in many cases commercially available or can be prepared byprocesses known from the literature, for example by halogenation ofcorresponding parent compounds or by elimination reactions oncorresponding alcohols or halides.

In this way, stilbene derivatives, for example, can be prepared. Thestilbenes can furthermore be prepared by reaction of a 4-substitutedbenzaldehyde with a corresponding phosphorus ylide by the Wittig method.However, tolans of the formula I can also be prepared by employingmono-substituted acetylene instead of the olefin (Synthesis 627 (1980)or Tetrahedron Lett. 27, 1171 (1986)).

For the coupling of aromatic compounds, it is furthermore possible toreact aryl halides with aryltin compounds. These reactions arepreferably carried out with addition of a catalyst, such as, forexample, a palladium(0) complex, in inert solvents, such ashydrocarbons, at high temperatures, for example in boiling xylene, undera protective gas.

Coupling reactions of alkynyl compounds with aryl halides can be carriedout analogously to the process described by A. O. King, E. Negishi, F.J. Villani and A. Silveira in J. Org. Chem. 43, 358 (1978).

Tolans of the formula I in which Z¹, Z², Z³ or Z⁴ is —C≡C— can also beprepared by the Fritsch-buttenberg-Wiechell rearrangement (Ann. 279,319, 1984), in which 1,1-diaryl-2-haloethylenes are rearranged to givediarylacetylenes in the presence of strong bases.

Tolans of the formula I can also be prepared by brominating thecorresponding stilbenes, followed by dehydrohalogenation. Use can bemade here of variants of this reaction which are known per se, but arenot mentioned here in greater detail.

Ethers of the formula I are obtainable by etherification ofcorresponding hydroxyl compounds, preferably corresponding phenols,where the hydroxyl compound is advantageously firstly converted into acorresponding metal derivative, for example into the correspondingalkali metal alkoxide or alkali metal phenoxide by treatment with NaH,NaNH₂, NaOH, KOH, Na₂CO₃ or K₂CO₃. This metal derivative can then bereacted with the appropriate alkyl halide, alkyl sulfonate or dialkylsulfate, advantageously in an inert solvent, such as, for example,acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide, oralternatively with an excess of aqueous or aqueous-alcoholic NaOH orKOH, at temperatures between about 20° C. and 100° C.

In order to prepare the laterally substituted fluorine or chlorinecompounds of the formula I, corresponding aniline derivatives can bereacted with sodium nitrite and either with tetrafluoroboric acid (inorder to introduce an F atom) or with copper(I) chloride (in order tointroduce a Cl atom) to give the diazonium salts, which are thenthermally decomposed at temperatures of 100–140° C.

The linking of an aromatic ring to a non-aromatic ring or of twonon-aromatic rings is preferably obtained by condensation of anorganolithium or organomagnesium compound with a ketone if an aliphaticgroup Z¹ is intended to be present between the rings.

The organometallic compounds are prepared, for example, by metal-halogenexchange (for example in accordance with Org. React. 6, 339–366 (1951))between the corresponding halogen compound and an organo-lithiumcompound, preferably tert-butyllithium or lithium naphthalenide, or byreaction with magnesium turnings.

The linking of two aromatic rings is preferably carried out byFriedel-Crafts alkylation or acylation by reacting the correspondingaromatic compounds with Lewis acid catalysis. Suitable Lewis acids are,for example, SnCl₄, ZnCl₂, AlCl₃ and TiCl₄.

Furthermore, the linking of two aromatic rings can be carried out by theUllmann reaction (for example Synthesis 1974, 9) between aryl iodidesand copper iodide, but preferably between an arylcopper compound and anaryl iodide, or by the Gomberg-Bachmann reaction between anaryldiazonium salt and the corresponding aromatic compound (for exampleOrg. React. 2, 224 (1944)).

The tolans of the formula I are prepared, for example, by reaction ofthe corresponding aryl halides with an acetylide in a basic solvent withtransition-metal catalysis; palladium catalysts can preferably be usedhere, in particular a mixture of bis(triphenylphosphine)palladium(II)chloride and copper iodide in piperidine as solvent.

In addition, the compounds of the formula I can be prepared by reducinga compound which conforms to the formula I, but contains one or morereducible groups and/or C—C bonds in place of H atoms.

Suitable reducible groups are preferably carbonyl groups, in particularketo groups, furthermore, for example, free or esterified hydroxylgroups or aromatically bound halogen atoms. Preferred starting materialsfor the reduction are compounds conforming to the formula I, but whichcontain a cyclohexene ring or cyclohexanone ring instead of acyclohexane ring and/or contain a —CH₂CH₂— group instead of a —CH═CH—group and/or contain a —CO— group instead of a —CH₂— group and/orcontain a free or functionally (for example in the form of itsp-toluenesulfonate) modified OH group instead of an H atom.

The reduction can be carried out, for example, by catalytichydrogenation at temperatures between about 0° C. and about 200° C. andpressures between about 1 and 200 bar in an inert solvent, for examplean alcohol, such as methanol, ethanol or isopropanol, an ether, such astetrahydrofuran (THF) or dioxane, an ester, such as ethyl acetate, acarboxylic acid, such as acetic acid, or a hydrocarbon, such ascyclohexane. Suitable catalysts are advantageously noble metals, such asPt or Pd, which can be employed in the form of oxides (for example PtO₂or PdO), on a support (for example Pd on carbon, calcium carbonate orstrontium, carbonate) or in finely divided form.

Ketones can also be reduced to the corresponding compounds of theformula I containing alkyl groups and/or —CH₂CH₂— bridges by the methodsof Clemmensen (using zinc, zinc amalgam or tin and hydrochloric acid,advantageously in aqueous-alcoholic solution or in the heterogeneousphase with water/toluene at temperatures between about 80 and 120° C.)or Wolff-Kishner (using hydrazine, advantageously in the presence ofalkali, such as KOH or NaOH, in a high-boiling solvent, such asdiethylene glycol or triethylene glycol, at temperatures between about100 and 200° C.).

Furthermore, reductions with complex hydrides are possible. For example,arylsulfonyloxy groups can be removed reductively using LiAlH₄, inparticular p-toluenesulfonyloxymethyl groups can be reduced to methylgroups, advantageously in an inert solvent, such as diethyl ether orTHF, at temperatures between about 0 and 100° C. Double bonds can behydrogenated using NaBH₄ or tributyltin hydride in methanol.

The starting materials are either known or can be prepared analogouslyto known compounds.

The liquid-crystalline media according to the invention preferablycomprise from 2 to 40, in particular from 4 to 30, components as furtherconstituents besides one or more compounds according to the invention.These media very particularly preferably comprise from 7 to 25components besides one or more compounds according to the invention.These further constituents are preferably selected from nematic ornematogenic (monotropic or isotropic) substances, in particularsubstances from the classes of the azoxybenzenes, benzylideneanilines,biphenyls, terphenyls, phenyl or cyclohexyl benzoates, phenyl orcyclohexyl esters of cyclohexanecarboxylic acid, phenyl or cyclohexylesters of cyclohexylbenzoic acid, phenyl or cyclohexyl esters ofcyclohexylcyclohexanecarboxylic acid, cyclohexylphenyl esters of benzoicacid, of cyclohexanecarboxylic acid or ofcyclohexylcyclohexanecarboxylic acid, phenylcyclohexanes,cyclohexylbiphenyls, phenylcyclohexylcyclohexanes,cyclohexylcyclohexanes, cyclohexylcyclohexylcyclohexenes,1,4-biscyclohexylbenzenes, 4,4′-biscyclohexylbiphenyls, phenyl- orcyclohexylpyrimidines, phenyl- or cyclohexylpyridines, phenyl- orcyclohexyldioxanes, phenyl- or cyclohexyl-1,3-dithianes,1,2-diphenylethanes, 1,2-dicyclohexylethanes,1-phenyl-2-cyclohexylethanes,1-cyclohexyl-2-(4-phenyl-cyclohexyl)ethanes,1-cyclohexyl-2-biphenylylethanes, 1-phenyl-2-cyclohexylphenylethanes,optionally halogenated stilbenes, benzyl phenyl ethers, tolans andsubstituted cinnamic acids. The 1,4-phenylene groups in these compoundsmay also be fluorinated.

The most important compounds suitable as further constituents of mediaaccording to the invention can be characterised by the formulae 1, 2, 3,4 and 5:R′—L—E—R″  1R′—L—COO—E—R″  2R′—L—OOC—E—R″  3R′—L—CH₂CH₂—E—R″  4R′—L—C≡C—E—R″  5

In the formulae 1, 2, 3, 4 and 5, L and E, which may be identical ordifferent, are each, independently of one another, a divalent radicalfrom the group formed by -Phe-, -Cyc-, -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-,-Pyr-, -Dio-, -G-Phe- and -G-Cyc- and their mirror images, where Phe isunsubstituted or fluorine-substituted 1,4-phenylene, cyc istrans-1,4-cyclohexylene or 1,4-cyclohexenylene, Pyr ispyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio is 1,3-dioxane-2,5-diyl,and G is 2-(trans-1,4-cyclohexyl)ethyl, pyrimidine-2,5-diyl,pyridine-2,5-diyl or 1,3-dioxane-2,5-diyl.

One of the radicals L and E is preferably Cyc, Phe or Pyr. E ispreferably Cyc, Phe or Phe-Cyc. The media according to the inventionpreferably comprise one or more components selected from the compoundsof the formulae 1, 2, 3, 4 and 5 in which L and E are selected from thegroup consisting of Cyc, Phe and Pyr and simultaneously one or morecomponents selected from the compounds of the formulae 1, 2, 3, 4 and 5in which one of the radicals L and E is selected from the groupconsisting of Cyc, Phe and Pyr and the other radical is selected fromthe group consisting of -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, -G-Phe- and-G-Cyc-, and optionally one or more components selected from thecompounds of the formulae 1, 2, 3, 4 and 5 in which the radicals L and Eare selected from the group consisting of -Phe-Cyc-, -Cyc-Cyc-, -G-Phe-and -G-Cyc-.

R′ and/or R″ are each, independently of one another, alkyl, alkenyl,alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbonatoms, —F, —Cl, —CN, —NCS or —(O)_(i)CH_(3−(k+l))F_(k)Cl_(l), where i is0 or 1 and k and l are 1, 2 or 3.

In a smaller sub-group of the compounds of the formulae 1, 2, 3, 4 and5, R′ and R″ are each, independently of one another, alkyl, alkenyl,alkoxy, alkoxyalkyl, alkenyloxy or alkanoyloxy having up to 8 carbonatoms. This smaller sub-group is called group A below, and the compoundsare referred to by the sub-formulae 1a, 2a, 3a, 4a and 5a. In most ofthese compounds, R′ and R″ are different from one another, one of theseradicals usually being alkyl, alkenyl, alkoxy or alkoxyalkyl.

In another smaller sub-group of the compounds of the formulae 1, 2, 3, 4and 5, which is known as group B, R″ is —F, —Cl, —NCS or—(O)_(i)CH_(3−(k+l))F_(k)Cl_(l), where i is 0 or 1, and k and l are 1, 2or 3; the compounds in which R″ has this meaning are referred to by thesub-formulae 1b, 2b, 3b, 4b and 5b. Particular preference is given tothose compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b in which R″ is—F, —Cl, —NCS, —CF₃, —OCHF₂ or —OCF₃.

In the compounds of the sub-formulae 1b, 2b, 3b, 4b and 5b, R′ is asdefined for the compounds of the sub-formulae 1a–5a and is preferablyalkyl, alkenyl, alkoxy or alkoxyalkyl.

In a further smaller sub-group of the compounds of the formulae 1, 2, 3,4 and 5, R″ is —CN; this sub-group is referred to below as group C, andthe compounds of this sub-group are correspondingly described bysub-formulae 1c, 2c, 3c, 4c and 5c. In the compounds of the sub-formulae1c, 2c, 3c, 4c and 5c, R′ is as defined for the compounds of thesub-formulae 1a–5a and is preferably alkyl, alkoxy or alkenyl.

Besides the preferred compounds of groups A, B and C, other compounds ofthe formulae 1, 2, 3, 4 and 5 having other variants of the proposedsubstituents are also customary. all these substances are obtainable bymethods which are known from the literature or analogously thereto.

Besides the compounds of the formula I according to the invention, themedia according to the invention preferably comprise one or morecompounds selected from group A and/or group B and/or group C. Theproportions by weight of the compounds from these groups in the mediaaccording to the invention are preferably

-   -   group A: from 0 to 90%, preferably from 20 to 90%, in particular        from 30 to 90%    -   group B: from 0 to 80%, preferably from 10 to 80%, in particular        from 10 to 65%    -   group C: from 0 to 80%, preferably from 5 to 80%, in particular        from 5 to 50%,        the sum of the proportions by weight of the group A and/or B        and/or C compounds present in the respective media according to        the invention preferably being 5% to 90% and in particular from        10% to 90%.

The media according to the invention preferably comprise from 1 to 40%,particularly preferably from 5 to 30%, of the compounds according to theinvention. Preference is furthermore given to media comprising more than40%, in particular from 45 to 90%, of compounds according to theinvention. The media preferably comprise three, four or five compoundsaccording to the invention.

The liquid-crystal mixtures which can be used in accordance with theinvention are prepared in a manner conventional per se. In general, thedesired amount of the components used in the lesser amount is dissolvedin the components making up the principal constituent, advantageously atelevated temperature. It is also possible to mix solutions of thecomponents in an organic solvent, for example in acetone, chloroform ormethanol, and to remove the solvent again, for example by distillation,after thorough mixing. It is furthermore possible to prepare themixtures in other conventional manners, for example by using premixes,for example homologue mixtures, or using so-called “multi-bottle”systems.

The dielectrics may also comprise further additives known to the personskilled in the art and described in the literature. For example, 0–15%,preferably 0–10%, of pleochroic dyes and/or chiral dopants can be added.The individual compounds added are employed in concentrations of from0.01 to 6%, preferably from 0.1 to 3%. However, the concentrationfigures for the other constituents of the liquid-crystal mixtures, i.e.of the liquid-crystalline or mesogenic compounds, are indicated withouttaking into account the concentration of these additives.

The following examples are intended to explain the invention withoutlimiting it. Above and below, percentages are per cent by weight. Alltemperatures are given in degrees Celsius.

“Conventional work-up” means that water is added if desired, the mixtureis extracted with methylene chloride, diethyl ether or toluene, thephases are separated, the organic phase is dried and evaporated, and theproduct is purified by distillation under reduced pressure orcrystallisation and/or chromatography.

WORKING EXAMPLES 1. Synthesis of2-butoxy-7-ethoxy-1,8,9,9-tetrafluorofluorene of the formula 8

1.1 Preparation of 1-bromo-3-fluoro-4-butoxybenzene (2)

0.315 mol of each of 4-bromo-2-fluorophenol (1), 1-butanol andtriphenylphosphine were dissolved in 1000 ml of tetrahydrofuran, and0.315 mol of diisopropyl azodicarboxylate was added dropwise at about20° C. After the mixture had been stirred overnight, the solvent wasremoved by distillation in a rotary evaporator, and the residue wassubjected to conventional work-up, giving the compound (2) in a yield of95.6% of theory.

1.2 Preparation of the Boron Compound (3)

0.180 mol of n-butyllithium (as a 15% solution in n-hexane) was addeddropwise at −70° C. to a solution of 0.162 mol of1-bromo-3-fluoro-4-butoxybenzene (2) in 540 ml of diethyl ether. Afterthe mixture had been stirred for 30 minutes, 0.180 mol of trimethylborate was added dropwise at −70° C., and the mixture was stirred for afurther 30 minutes. The reaction mixture warmed to 20° C. was hydrolysedwith water and acidified with 2 molar hydrochloric acid, and methyltert-butyl ether was added. The mixture was subjected to, conventionalwork-up, giving the compound (3) as a white solid.

1.3 Cross-coupling to give 4-ethoxy-3,3′-difluoro-4′-butoxybiphenyl (5)

10 ml of tetrahydrofuran, 0.628 mmol of bis(triphenylphosphine)palladiumdichloride and 0.630 mmol of hydrazinium hydroxide were added to 24.1mmol of sodium metaborate octahydrate in 12.6 ml of H₂O, and the mixturewas stirred at room temperature for 5 minutes. 32.1 mmol of the boroncompound (3), 32.1 mmol of 1-bromo-3-fluoro-4-ethoxybenzene (4)(prepared analogously to Example 1.1) and 30 ml of tetrahydrofuran werethen added, and the mixture was heated under reflux conditions for 6hours. After subsequent cooling, the organic phase was separated off andsubjected to conventional work-up.

1.4 Preparation of the Fluorenone Derivative (6)

60 mmol of 4-ethoxy-3,3′-difluoro-4′-butoxybiphenyl (5) are introducedinto 200 ml of tetrahydrofuran, and the mixture is cooled to −70° C. 120mmol of a 1.6 M solution of n-butyllithium in hexane are added dropwise,and the mixture is stirred at this temperature for 2 hours. 60 mmol ofdimethyl carbonate are subsequently added rapidly with vigorousstirring, the mixture is stirred at −70° C. for a further hour, allowedto warm to 0° C., hydrolysed with dilute hydrochloric acid and subjectedto conventional work-up.

1.5 Preparation of the Dithioketal Compound (7)

30 mmol of the fluorenone derivative (6) are dissolved in 100 ml ofdiethyl ether, 60 mmol of 1,2-ethanediol and 45 mmol of borontrifluoride etherate are added, and the mixture is heated overnightunder reflux conditions. After cooling, the mixture is subjected toconventional work-up, giving 27.5 mmol (92%) of the dithioketal (7).

1.6 Oxidative Fluorodesulfurisation to Give the Fluorene Derivative (8)

11 mmol of 1,3-dibromo-5,5-dimethylhydantoin are dissolved in 50 ml ofdichloromethane, and the mixture is cooled to −70° C. 29 mmol ofhydrogen fluoride in pyridine (65%) are added. 11 mmol of thedithioketal (7) dissolved in 50 ml of dichloromethane are added dropwiseover the course of 20 minutes, and the mixture is allowed to warm to−60° C. after one hour. The reaction mixture is poured into saturatedsodium hydrogencarbonate solution and then subjected to conventionalwork-up, giving the fluorene derivative (8). (Δε=−21.2, Δn=0.204).

For comparison, measurements are made on the difluorinated compound2-butoxy-7-ethoxy-9,9-difluorofluorene obtainable analogously: Δε=−9.1,Δn=0.225.

2. Synthesis of 2-butoxy-7-ethoxy-1,8,9-trifluoro-9H-fluorene of theformula 9

20 mmol of the fluorenone compound (6) (obtainable in accordance withExample 1.4) are dissolved in 100 ml of isopropanol, and 8 mmol ofsodium borohydride are added. The mixture is stirred at room temperaturefor 3 hours and subjected to conventional work-up. The crude product isdissolved in 300 ml of dichloromethane and cooled to 0° C. 20 mmol ofdiethylaminosulfur trifluoride are added dropwise, and the mixture issubjected to conventional work-up, giving the 9H-fluorene (9).(Δε=−15.3, Δn=0.214).

For comparison, measurements are made on the monofluorinated compound2-butoxy-7-ethoxy-9-fluoro-9H-fluorene obtainable analogously: Δε=−4.7,Δn=0.238.

3. Synthesis of 2-butoxy-7-ethoxy-1,8-difluoro-9,9H-fluorene of theformula 10

27 mmol of the fluorenone compound (6) (obtainable in accordance withExample 1.4), 13 mmol of sodium borohydride and 74 mmol of aluminiumchloride are suspended in 250 ml of tetrahydrofuran, and the mixture isheated under reflux conditions for 2 hours. Conventional work-up gives23.4 mmol (87%) of the 9,9H-fluorene (10). (Δε=−8.7, Δn=0.226).

For comparison, measurements are made on the unfluorinated compound2-butoxy-7-ethoxy-9,9H-fluorene obtainable analogously: Δε=−0.5,Δn=0.253.

4. Synthesis of the 1,8,9,9-tetrafluorofluorene compound of the formula20

4.1 Preparation of 1-bromo-2′,3′-difluoro-4′-ethoxybiphenyl (13)

0.450 mol of sodium metaborate are introduced into 240 ml of water.0.012 mol of bis(triphenylphosphine)palladium(II) chloride, 0.6 mol of4-bromo-1-iodobenzene (11) and 0.012 mol of hydrazinium hydrochlorideare added, and the mixture is stirred at about 20° C. for 5 minutes. 0.6mol of 2,3-difluoro-4-ethoxyphenylboronic acid (12) dissolved in 600 mlof tetrahydrofuran are then added, and the mixture is refluxed for 4hours, giving the compound of the formula 13.

4.2 Preparation of the Boronic Acid Compound (14)

0.09 mol of 1-bromo-2′,3′-difluoro-4′-ethoxybiphenyl (13) is dissolvedin 200 ml of diethyl ether, and the mixture is cooled to −70° C. 0.095mol of butyllithium is added dropwise at this temperature, and themixture is stirred for a further 45 minutes. 0.1 mol of trimethyl borateis then added, and the mixture is stirred for 30 minutes and, afterwarming to about 20° C., subjected to conventional work-up.

4.3 Preparation of the Terphenyl Compound (16)

0.047 mol of 2′,3′-difluoro-4′-ethoxybiphenylboronic acid (14), 0.05 molof 1-bromo-3-fluoro-4-iodobenzene (15), 1 mmol of palladium acetate, 2mmol of triphenylphosphine, 25 ml of saturated sodium carbonatesolution, 20 ml of water and 100 ml of isopropanol are initiallyintroduced and refluxed overnight. Conventional work-up gives theterphenyl compound (16).

4.4 Preparation of the Compound of the Formula 18

The preparation is carried out analogously to Example 1.3 using theterphenyl compound (16) and 3-fluoro-4-ethoxyphenylboronic acid (17).

4.5 Preparation of the Fluorenone Compound (19)

The synthesis is carried out analogously to Example 1.4 using thecompound (18) obtained previously.

4.6 Preparation of the 1,8,9,9-tetrafluorofluorene compound (20)

The compound (20) is obtained in the final step analogously to Examples1.5 and 1.6 by oxidative fluorodesulfurisation of the compound (19)(Δε=−28.8, Δn 0.282).

Fluorene compounds of the following formula

are obtained analogously to Examples 1.1 to 1.6, in particular 1.5 and1.6:

R¹ R² L¹ L² (21) —C₃H₇ —C₃H₇ —H —F (22) —C₃H₇ —C₄H₉ —H —F (23) —C₃H₇—C₅H₁₁ —H —F (24) —C₃H₇ —OC₂H₅ —H —F (25) —C₃H₇ —OC₃H₇ —H —F (26) —C₃H₇—OC₄H₉ —H —F (27) —C₃H₇ —OC₅H₁₁ —H —F (28) —C₄H₉ —C₃H₇ —H —F (29) —C₄H₉—C₄H₉ —H —F (30) —C₄H₉ —C₅H₁₁ —H —F (31) —C₄H₉ —OC₂H₅ —H —F (32) —C₄H₉—OC₃H₇ —H —F (33) —C₄H₉ —OC₄H₉ —H —F (34) —C₄H₉ —OC₅H₁₁ —H —F (35)—C₅H₁₁ —C₃H₇ —H —F (36) —C₅H₁₁ —C₄H₉ —H —F (37) —C₅H₁₁ —C₅H₁₁ —H —F (38)—C₅H₁₁ —OC₂H₅ —H —F (39) —C₅H₁₁ —OC₃H₇ —H —F (40) —C₅H₁₁ —OC₄H₉ —H —F(41) —C₅H₁₁ —OC₅H₁₁ —H —F (42) —CH═CH₂ —C₃H₇ —H —F (43) —CH═CH₂ —C₄H₉ —H—F (44) —CH═CH₂ —C₅H₁₁ —H —F (45) —CH═CH₂ —CH═CH₂ —H —F (46) —CH═CH₂—CH═CH—CH₃ —H —F (47) —CH═CH₂ —CH₂—CH═CH—CH₃ —H —F (48) —CH═CH₂—C₂H₄—CH═CH₂ —H —F (49) —CH═CH₂ —C₂H₄—CH═CH—CH₃ —H —F (50) —CH═CH₂—OC₂H₅ —H —F (51) —CH═CH₂ —OC₃H₇ —H —F (52) —CH═CH₂ —OC₄H₉ —H —F (53)—CH═CH₂ —OC₅H₁₁ —H —F (54) —CH═CH—CH₃ —C₃H₇ —H —F (55) —CH═CH—CH₃ —C₄H₉—H —F (56) —CH═CH—CH₃ —C₅H₁₁ —H —F (57) —CH═CH—CH₃ —CH═CH₂ —H —F (58)—CH═CH—CH₃ —CH═CH—CH₃ —H —F (59) —CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H —F (60)—CH═CH—CH₃ —C₂H₄—CH═CH₂ —H —F (61) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —H —F (62)—CH═CH—CH₃ —OC₂H₅ —H —F (63) —CH═CH—CH₃ —OC₃H₇ —H —F (64) —CH═CH—CH₃—OC₄H₉ —H —F (65) —CH═CH—CH₃ —OC₅H₁₁ —H —F (66) —CH₂—CH═CH—CH₃ —C₃H₇ —H—F (67) —CH₂—CH═CH—CH₃ —C₄H₉ —H —F (68) —CH₂—CH═CH—CH₃ —C₅H₁₁ —H —F (69)—CH₂—CH═CH—CH₃ —CH═CH₂ —H —F (70) —CH₂—CH═CH—CH₃ —CH═CH—CH₃ —H —F (71)—CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H —F (72) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH₂ —H—F (73) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —H —F (74) —CH₂—CH═CH—CH₃ —OC₂H₅—H —F (75) —CH₂—CH═CH—CH₃ —OC₃H₇ —H —F (76) —CH₂—CH═CH—CH₃ —OC₄H₉ —H —F(77) —CH₂—CH═CH—CH₃ —OC₅H₁₁ —H —F (78) —C₂H₄—CH═CH₂ —C₃H₇ —H —F (79)—C₂H₄—CH═CH₂ —C₄H₉ —H —F (80) —C₂H₄—CH═CH₂ —C₅H₁₁ —H —F (81)—C₂H₄—CH═CH₂ —CH═CH₂ —H —F (82) —C₂H₄—CH═CH₂ —CH═CH—CH₃ —H —F (83)—C₂H₄—CH═CH₂ —CH₂—CH═CH—CH₃ —H —F (84) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —H —F(85) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH—CH₃ —H —F (86) —C₂H₄—CH═CH₂ —OC₂H₅ —H —F(87) —C₂H₄—CH═CH₂ —OC₃H₇ —H —F (88) —C₂H₄—CH═CH₂ —OC₄H₉ —H —F (89)—C₂H₄—CH═CH₂ —OC₅H₁₁ —H —F (90) —C₂H₄—CH═CH—CH₃ —C₃H₇ —H —F (91)—C₂H₄—CH═CH—CH₃ —C₄H₉ —H —F (92) —C₂H₄—CH═CH—CH₃ —C₅H₁₁ —H —F (93)—C₂H₄—CH═CH—CH₃ —CH═CH₂ —H —F (94) —C₂H₄—CH═CH—CH₃ —CH═CH—CH₃ —H —F (95)—C₂H₄—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H —F (96) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH₂—H —F (97) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —H —F (98) —C₂H₄—CH═CH—CH₃—OC₂H₅ —H —F (99) —C₂H₄—CH═CH—CH₃ —OC₃H₇ —H —F (100) —C₂H₄—CH═CH—CH₃—OC₄H₉ —H —F (101) —C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —H —F (102) —OC₂H₅ —C₃H₇ —H—F (103) —OC₂H₅ —C₄H₉ —H —F (104) —OC₂H₅ —C₅H₁₁ —H —F (105) —OC₂H₅—OC₂H₅ —H —F (106) —OC₂H₅ —OC₃H₇ —H —F (107) —OC₂H₅ —OC₄H₉ —H —F (108)—OC₂H₅ —OC₅H₁₁ —H —F (109) —OC₃H₇ —C₃H₇ —H —F (110) —OC₃H₇ —C₄H₉ —H —F(111) —OC₃H₇ —C₅H₁₁ —H —F (112) —OC₃H₇ —OC₂H₅ —H —F (113) —OC₃H₇ —OC₃H₇—H —F (114) —OC₃H₇ —OC₄H₉ —H —F (115) —OC₃H₇ —OC₅H₁₁ —H —F (116) —OC₄H₉—C₃H₇ —H —F (117) —OC₄H₉ —C₄H₉ —H —F (118) —OC₄H₉ —C₅H₁₁ —H —F (119)—OC₄H₉ —OC₂H₅ —H —F (120) —OC₄H₉ —OC₃H₇ —H —F (121) —OC₄H₉ —OC₄H₉ —H —F(122) —OC₄H₉ —OC₅H₁₁ —H —F (123) —OC₅H₁₁ —C₃H₇ —H —F (124) —OC₅H₁₁ —C₄H₉—H —F (125) —OC₅H₁₁ —C₅H₁₁ —H —F (126) —OC₅H₁₁ —OC₂H₅ —H —F (127)—OC₅H₁₁ —OC₃H₇ —H —F (128) —OC₅H₁₁ —OC₄H₉ —H —F (129) —OC₅H₁₁ —OC₅H₁₁ —H—F (130) —C₃H₇ —C₃H₇ —H —CF₃ (131) —C₃H₇ —C₄H₉ —H —CF₃ (132) —C₃H₇—C₅H₁₁ —H —CF₃ (133) —C₃H₇ —OC₂H₅ —H —CF₃ (134) —C₃H₇ —OC₃H₇ —H —CF₃(135) —C₃H₇ —OC₄H₉ —H —CF₃ (136) —C₃H₇ —OC₅H₁₁ —H —CF₃ (137) —C₄H₉ —C₃H₇—H —CF₃ (138) —C₄H₉ —C₄H₉ —H —CF₃ (139) —C₄H₉ —C₅H₁₁ —H —CF₃ (140) —C₄H₉—OC₂H₅ —H —CF₃ (141) —C₄H₉ —OC₃H₇ —H —CF₃ (142) —C₄H₉ —OC₄H₉ —H —CF₃(143) —C₄H₉ —OC₅H₁₁ —H —CF₃ (144) —C₅H₁₁ —C₃H₇ —H —CF₃ (145) —C₅H₁₁—C₄H₉ —H —CF₃ (146) —C₅H₁₁ —C₅H₁₁ —H —CF₃ (147) —C₅H₁₁ —OC₂H₅ —H —CF₃(148) —C₅H₁₁ —OC₃H₇ —H —CF₃ (149) —C₅H₁₁ —OC₄H₉ —H —CF₃ (150) —C₅H₁₁—OC₅H₁₁ —H —CF₃ (151) —OC₂H₅ —C₃H₇ —H —CF₃ (152) —OC₂H₅ —C₄H₉ —H —CF₃(153) —OC₂H₅ —C₅H₁₁ —H —CF₃ (154) —OC₂H₅ —OC₂H₅ —H —CF₃ (155) —OC₂H₅—OC₃H₇ —H —CF₃ (156) —OC₂H₅ —OC₄H₉ —H —CF₃ (157) —OC₂H₅ —OC₅H₁₁ —H —CF₃(158) —OC₃H₇ —C₃H₇ —H —CF₃ (159) —OC₃H₇ —C₄H₉ —H —CF₃ (160) —OC₃H₇—C₅H₁₁ —H —CF₃ (161) —OC₃H₇ —OC₂H₅ —H —CF₃ (162) —OC₃H₇ —OC₃H₇ —H —CF₃(163) —OC₃H₇ —OC₄H₉ —H —CF₃ (164) —OC₃H₇ —OC₅H₁₁ —H —CF₃ (165) —OC₄H₉—C₃H₇ —H —CF₃ (166) —OC₄H₉ —C₄H₉ —H —CF₃ (167) —OC₄H₉ —C₅H₁₁ —H —CF₃(168) —OC₄H₉ —OC₂H₅ —H —CF₃ (169) —OC₄H₉ —OC₃H₇ —H —CF₃ (170) —OC₄H₉—OC₄H₉ —H —CF₃ (171) —OC₄H₉ —OC₅H₁₁ —H —CF₃ (172) —OC₅H₁₁ —C₃H₇ —H —CF₃(173) —OC₅H₁₁ —C₄H₉ —H —CF₃ (174) —OC₅H₁₁ —C₅H₁₁ —H —CF₃ (175) —OC₅H₁₁—OC₂H₅ —H —CF₃ (176) —OC₅H₁₁ —OC₃H₇ —H —CF₃ (177) —OC₅H₁₁ —OC₄H₉ —H —CF₃(178) —OC₅H₁₁ —OC₅H₁₁ —H —CF₃ (179) —C₃H₇ —C₃H₇ —F —CF₃ (180) —C₃H₇—C₄H₉ —F —CF₃ (181) —C₃H₇ —C₅H₁₁ —F —CF₃ (182) —C₃H₇ —OC₂H₅ —F —CF₃(183) —C₃H₇ —OC₃H₇ —F —CF₃ (184) —C₃H₇ —OC₄H₉ —F —CF₃ (185) —C₃H₇—OC₅H₁₁ —F —CF₃ (186) —C₄H₉ —C₃H₇ —F —CF₃ (187) —C₄H₉ —C₄H₉ —F —CF₃(188) —C₄H₉ —C₅H₁₁ —F —CF₃ (189) —C₄H₉ —OC₂H₅ —F —CF₃ (190) —C₄H₉ —OC₃H₇—F —CF₃ (191) —C₄H₉ —OC₄H₉ —F —CF₃ (192) —C₄H₉ —OC₅H₁₁ —F —CF₃ (193)—C₅H₁₁ —C₃H₇ —F —CF₃ (194) —C₅H₁₁ —C₄H₉ —F —CF₃ (195) —C₅H₁₁ —C₅H₁₁ —F—CF₃ (196) —C₅H₁₁ —OC₂H₅ —F —CF₃ (197) —C₅H₁₁ —OC₃H₇ —F —CF₃ (198)—C₅H₁₁ —OC₄H₉ —F —CF₃ (199) —C₅H₁₁ —OC₅H₁₁ —F —CF₃ (200) —CH═CH₂ —C₃H₇—F —CF₃ (201) —CH═CH₂ —C₄H₉ —F —CF₃ (202) —CH═CH₂ —C₅H₁₁ —F —CF₃ (203)—CH═CH₂ —CH═CH₂ —F —CF₃ (204) —CH═CH₂ —CH═CH—CH₃ —F —CF₃ (205) —CH═CH₂—CH₂—CH═CH—CH₃ —F —CF₃ (206) —CH═CH₂ —C₂H₄—CH═CH₂ —F —CF₃ (207) —CH═CH₂—C₂H₄—CH═CH—CH₃ —F —CF₃ (208) —CH═CH₂ —OC₂H₅ —F —CF₃ (209) —CH═CH₂—OC₃H₇ —F —CF₃ (210) —CH═CH₂ —OC₄H₉ —F —CF₃ (211) —CH═CH₂ —OC₅H₁₁ —F—CF₃ (212) —CH═CH—CH₃ —C₃H₇ —F —CF₃ (213) —CH═CH—CH₃ —C₄H₉ —F —CF₃ (214)—CH═CH—CH₃ —C₅H₁₁ —F —CF₃ (215) —CH═CH—CH₃ —CH═CH₂ —F —CF₃ (216)—CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃ (217) —CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —CF₃(218) —CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —CF₃ (219) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃—F —CF₃ (220) —CH═CH—CH₃ —OC₂H₅ —F —CF₃ (221) —CH═CH—CH₃ —OC₃H₇ —F —CF₃(222) —CH═CH—CH₃ —OC₄H₉ —F —CF₃ (223) —CH═CH—CH₃ —OC₅H₁₁ —F —CF₃ (224)—CH₂—CH═CH—CH₃ —C₃H₇ —F —CF₃ (225) —CH₂—CH═CH—CH₃ —C₄H₉ —F —CF₃ (226)—CH₂—CH═CH—CH₃ —C₅H₁₁ —F —CF₃ (227) —CH₂—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (228)—CH₂—CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃ (229) —CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F—CF₃ (230) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —CF₃ (231) —CH₂—CH═CH—CH₃—C₂H₄—CH═CH—CH₃ —F —CF₃ (232) —CH₂—CH═CH—CH₃ —OC₂H₅ —F —CF₃ (233)—CH₂—CH═CH—CH₃ —OC₃H₇ —F —CF₃ (234) —CH₂—CH═CH—CH₃ —OC₄H₉ —F —CF₃ (235)—CH₂—CH═CH—CH₃ —OC₅H₁₁ —F —CF₃ (236) —C₂H₄—CH═CH₂ —C₃H₇ —F —CF₃ (237)—C₂H₄—CH═CH₂ —C₄H₉ —F —CF₃ (238) —C₂H₄—CH═CH₂ —C₅H₁₁ —F —CF₃ (239)—C₂H₄—CH═CH₂ —CH═CH₂ —F —CF₃ (240) —C₂H₄—CH═CH₂ —CH═CH—CH₃ —F —CF₃ (241)—C₂H₄—CH═CH₂ —CH₂—CH═CH—CH₃ —F —CF₃ (242) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —F—CF₃ (243) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH—CH₃ —F —CF₃ (244) —C₂H₄—CH═CH₂—OC₂H₅ —F —CF₃ (245) —C₂H₄—CH═CH₂ —OC₃H₇ —F —CF₃ (246) —C₂H₄—CH═CH₂—OC₄H₉ —F —CF₃ (247) —C₂H₄—CH═CH₂ —OC₅H₁₁ —F —CF₃ (248) —C₂H₄—CH═CH—CH₃—C₃H₇ —F —CF₃ (249) —C₂H₄—CH═CH—CH₃ —C₄H₉ —F —CF₃ (250) —C₂H₄—CH═CH—CH₃—C₅H₁₁ —F —CF₃ (251) —C₂H₄—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (252)—C₂H₄—CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃ (253) —C₂H₄—CH═CH—CH₃ —CH₂—CH═CH—CH₃—F —CF₃ (254) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —CF₃ (255) —C₂H₄—CH═CH—CH₃—C₂H₄—CH═CH—CH₃ —F —CF₃ (256) —C₂H₄—CH═CH—CH₃ —OC₂H₅ —F —CF₃ (257)—C₂H₄—CH═CH—CH₃ —OC₃H₇ —F —CF₃ (258) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —F —CF₃(259) —C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —F —CF₃ (260) —OC₂H₅ —C₃H₇ —F —CF₃ (261)—OC₂H₅ —C₄H₉ —F —CF₃ (262) —OC₂H₅ —C₅H₁₁ —F —CF₃ Δε = −17.4; Δn = 0.159(263) —OC₂H₅ —OC₂H₅ —F —CF₃ (264) —OC₂H₅ —OC₃H₇ —F —CF₃ (265) —OC₂H₅—OC₄H₉ —F —CF₃ (266) —OC₂H₅ —OC₅H₁₁ —F —CF₃ (267) —OC₃H₇ —C₃H₇ —F —CF₃(268) —OC₃H₇ —C₄H₉ —F —CF₃ (269) —OC₃H₇ —C₅H₁₁ —F —CF₃ (270) —OC₃H₇—OC₂H₅ —F —CF₃ (271) —OC₃H₇ —OC₃H₇ —F —CF₃ (272) —OC₃H₇ —OC₄H₉ —F —CF₃(273) —OC₃H₇ —OC₅H₁₁ —F —CF₃ (274) —OC₄H₉ —C₃H₇ —F —CF₃ (275) —OC₄H₉—C₄H₉ —F —CF₃ (276) —OC₄H₉ —C₅H₁₁ —F —CF₃ (277) —OC₄H₉ —OC₂H₅ —F —CF₃(278) —OC₄H₉ —OC₃H₇ —F —CF₃ (279) —OC₄H₉ —OC₄H₉ —F —CF₃ (280) —OC₄H₉—OC₅H₁₁ —F —CF₃ (281) —OC₅H₁₁ —C₃H₇ —F —CF₃ (282) —OC₅H₁₁ —C₄H₉ —F —CF₃(283) —OC₅H₁₁ —C₅H₁₁ —F —CF₃ (284) —OC₅H₁₁ —OC₂H₅ —F —CF₃ (285) —OC₅H₁₁—OC₃H₇ —F —CF₃ (286) —OC₅H₁₁ —OC₄H₉ —F —CF₃ (287) —OC₅H₁₁ —OC₅H₁₁ —F—CF₃ (288) —C₃H₇ —C₃H₇ —F —F (289) —C₃H₇ —C₄H₉ —F —F (290) —C₃H₇ —C₅H₁₁—F —F Δε = −9.0; Δn = 0.155 (291) —C₃H₇ —OC₂H₅ —F —F (292) —C₃H₇ —OC₃H₇—F —F (293) —C₃H₇ —OC₄H₉ —F —F (294) —C₃H₇ —OC₅H₁₁ —F —F (295) —C₄H₉—C₄H₉ —F —F (296) —C₄H₉ —C₅H₁₁ —F —F (297) —C₄H₉ —OC₂H₅ —F —F (298)—C₄H₉ —OC₃H₇ —F —F (299) —C₄H₉ —OC₄H₉ —F —F (300) —C₄H₉ —OC₅H₁₁ —F —F(301) —C₅H₁₁ —C₅H₁₁ —F —F (302) —C₅H₁₁ —OC₂H₅ —F —F Δε = −13.7; Δn =0.178 (303) —C₅H₁₁ —OC₃H₇ —F —F (304) —C₅H₁₁ —OC₄H₉ —F —F (305) —C₅H₁₁—OC₅H₁₁ —F —F (306) —CH═CH₂ —C₃H₇ —F —F (307) —CH═CH₂ —C₄H₉ —F —F (308)—CH═CH₂ —C₅H₁₁ —F —F (309) —CH═CH₂ —CH═CH₂ —F —F (310) —CH═CH₂—CH═CH—CH₃ —F —F (311) —CH═CH₂ —CH₂—CH═CH—CH₃ —F —F (312) —CH═CH₂—C₂H₄—CH═CH₂ —F —F (313) —CH═CH₂ —C₂H₄—CH═CH—CH₃ —F —F (314) —CH═CH₂—OC₂H₅ —F —F (315) —CH═CH₂ —OC₃H₇ —F —F (316) —CH═CH₂ —OC₄H₉ —F —F (317)—CH═CH₂ —OC₅H₁₁ —F —F (318) —CH═CH—CH₃ —C₃H₇ —F —F (319) —CH═CH—CH₃—C₄H₉ —F —F (320) —CH═CH—CH₃ —C₅H₁₁ —F —F (321) —CH═CH—CH₃ —CH═CH—CH₃ —F—F (322) —CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —F (323) —CH═CH—CH₃ —C₂H₄—CH═CH₂—F —F (324) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F (325) —CH═CH—CH₃ —OC₂H₅ —F—F (326) —CH═CH—CH₃ —OC₃H₇ —F —F (327) —CH═CH—CH₃ —OC₄H₉ —F —F (328)—CH═CH—CH₃ —OC₅H₁₁ —F —F (329) —CH₂—CH═CH—CH₃ —C₃H₇ —F —F (330)—CH₂—CH═CH—CH₃ —C₄H₉ —F —F (331) —CH₂—CH═CH—CH₃ —C₅H₁₁ —F —F (332)—CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —F (333) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH₂ —F—F (334) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F (335) —CH₂—CH═CH—CH₃—OC₂H₅ —F —F (336) —CH₂—CH═CH—CH₃ —OC₃H₇ —F —F (337) —CH₂—CH═CH—CH₃—OC₄H₉ —F —F (338) —CH₂—CH═CH—CH₃ —OC₅H₁₁ —F —F (339) —C₂H₄—CH═CH₂ —C₃H₇—F —F (340) —C₂H₄—CH═CH₂ —C₄H₉ —F —F (341) —C₂H₄—CH═CH₂ —C₅H₁₁ —F —F(342) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —F —F (343) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH—CH₃—F —F (344) —C₂H₄—CH═CH₂ —OC₂H₅ —F —F (345) —C₂H₄—CH═CH₂ —OC₃H₇ —F —F(346) —C₂H₄—CH═CH₂ —OC₄H₉ —F —F (347) —C₂H₄—CH═CH₂ —OC₅H₁₁ —F —F (348)—C₂H₄—CH═CH—CH₃ —C₃H₇ —F —F (349) —C₂H₄—CH═CH—CH₃ —C₄H₉ —F —F (350)—C₂H₄—CH═CH—CH₃ —C₅H₁₁ —F —F (351) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F(352) —C₂H₄—CH═CH—CH₃ —OC₂H₅ —F —F (353) —C₂H₄—CH═CH—CH₃ —OC₃H₇ —F —F(354) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —F —F (355) —C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —F —F(356) —OC₂H₅ —OC₂H₅ —F —F (357) —OC₂H₅ —OC₃H₇ —F —F (358) —OC₂H₅ —OC₄H₉—F —F (359) —OC₂H₅ —OC₅H₁₁ —F —F (360) —OC₃H₇ —OC₃H₇ —F —F (361) —OC₃H₇—OC₄H₉ —F —F (362) —OC₃H₇ —OC₅H₁₁ —F —F (363) —OC₄H₉ —OC₄H₉ —F —F (364)—OC₄H₉ —OC₅H₁₁ —F —F (365) —OC₅H₁₁ —OC₅H₁₁ —F —F (366) —C₃H₇ —C₃H₇ —CF₃—CF₃ (367) —C₃H₇ —C₄H₉ —CF₃ —CF₃ (368) —C₃H₇ —C₅H₁₁ —CF₃ —CF₃ (369)—C₃H₇ —OC₂H₅ —CF₃ —CF₃ (370) —C₃H₇ —OC₃H₇ —CF₃ —CF₃ (371) —C₃H₇ —OC₄H₉—CF₃ —CF₃ (372) —C₃H₇ —OC₅H₁₁ —CF₃ —CF₃ (373) —C₄H₉ —C₄H₉ —CF₃ —CF₃(374) —C₄H₉ —C₅H₁₁ —CF₃ —CF₃ (375) —C₄H₉ —OC₂H₅ —CF₃ —CF₃ (376) —C₄H₉—OC₃H₇ —CF₃ —CF₃ (377) —C₄H₉ —OC₄H₉ —CF₃ —CF₃ (378) —C₄H₉ —OC₅H₁₁ —CF₃—CF₃ (379) —C₅H₁₁ —C₅H₁₁ —CF₃ —CF₃ (380) —C₅H₁₁ —OC₂H₅ —CF₃ —CF₃ (381)—C₅H₁₁ —OC₃H₇ —CF₃ —CF₃ (382) —C₅H₁₁ —OC₄H₉ —CF₃ —CF₃ (383) —C₅H₁₁—OC₅H₁₁ —CF₃ —CF₃ (384) —OC₂H₅ —OC₂H₅ —CF₃ —CF₃ (385) —OC₂H₅ —OC₃H₇ —CF₃—CF₃ (386) —OC₂H₅ —OC₄H₉ —CF₃ —CF₃ (387) —OC₂H₅ —OC₅H₁₁ —CF₃ —CF₃ (388)—OC₃H₇ —OC₃H₇ —CF₃ —CF₃ (389) —OC₃H₇ —OC₄H₉ —CF₃ —CF₃ (390) —OC₃H₇—OC₅H₁₁ —CF₃ —CF₃ (391) —OC₄H₉ —OC₄H₉ —CF₃ —CF₃ (392) —OC₄H₉ —OC₅H₁₁—CF₃ —CF₃ (393) —OC₅H₁₁ —OC₅H₁₁ —CF₃ —CF₃

Fluorene compounds of the following formulae

are obtained analogously to Example 2:

R¹ R² L¹ L² (400) —C₃H₇ —C₃H₇ —H —F (401) —C₃H₇ —C₄H₉ —H —F (402) —C₃H₇—C₅H₁₁ —H —F (403) —C₃H₇ —OC₂H₅ —H —F (404) —C₃H₇ —OC₃H₇ —H —F (405)—C₃H₇ —OC₄H₉ —H —F (406) —C₃H₇ —OC₅H₁₁ —H —F (407) —C₄H₉ —C₃H₇ —H —F(408) —C₄H₉ —C₄H₉ —H —F (409) —C₄H₉ —C₅H₁₁ —H —F (410) —C₄H₉ —OC₂H₅ —H—F (411) —C₄H₉ —OC₃H₇ —H —F (412) —C₄H₉ —OC₄H₉ —H —F (413) —C₄H₉ —OC₅H₁₁—H —F (414) —C₅H₁₁ —C₃H₇ —H —F (415) —C₅H₁₁ —C₄H₉ —H —F (416) —C₅H₁₁—C₅H₁₁ —H —F (417) —C₅H₁₁ —OC₂H₅ —H —F (418) —C₅H₁₁ —OC₃H₇ —H —F (419)—C₅H₁₁ —OC₄H₉ —H —F (420) —C₅H₁₁ —OC₅H₁₁ —H —F (421) —CH═CH₂ —C₃H₇ —H —F(422) —CH═CH₂ —C₄H₉ —H —F (423) —CH═CH₂ —C₅H₁₁ —H —F (424) —CH═CH₂—CH═CH₂ —H —F (425) —CH═CH₂ —CH═CH—CH₃ —H —F (426) —CH═CH₂—CH₂—CH═CH—CH₃ —H —F (427) —CH═CH₂ —C₂H₄—CH═CH₂ —H —F (428) —CH═CH₂—C₂H₄—CH═CH—CH3 —H —F (429) —CH═CH₂ —OC₂H₅ —H —F (430) —CH═CH₂ —OC₃H₇ —H—F (431) —CH═CH₂ —OC₄H₉ —H —F (432) —CH═CH₂ —OC₅H₁₁ —H —F (433)—CH═CH—CH₃ —C₃H₇ —H —F (434) —CH═CH—CH₃ —C₄H₉ —H —F (435) —CH═CH—CH₃—C₅H₁₁ —H —F (436) —CH═CH—CH₃ —CH═CH₂ —H —F (437) —CH═CH—CH₃ —CH═CH—CH₃—H —F (438) —CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H —F (439) —CH═CH—CH₃—C₂H₄—CH═CH₂ —H —F (440) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —H —F (441)—CH═CH—CH₃ —OC₂H₅ —H —F (442) —CH═CH—CH₃ —OC₃H₇ —H —F (443) —CH═CH—CH₃—OC₄H₉ —H —F (444) —CH═CH—CH₃ —OC₅H₁₁ —H —F (445) —CH₂—CH═CH—CH₃ —C₃H₇—H —F (446) —CH₂—CH═CH—CH₃ —C₄H₉ —H —F (447) —CH₂—CH═CH—CH₃ —C₅H₁₁ —H —F(448) —CH₂—CH═CH—CH₃ —CH═CH₂ —H —F (449) —CH₂—CH═CH—CH₃ —CH═CH—CH₃ —H —F(450) —CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H —F (451) —CH₂—CH═CH—CH₃—C₂H₄—CH═CH₂ —H —F (452) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —H —F (453)—CH₂—CH═CH—CH₃ —OC₂H₅ —H —F (454) —CH₂—CH═CH—CH₃ —OC₃H₇ —H —F (455)—CH₂—CH═CH—CH₃ —OC₄H₉ —H —F (456) —CH₂—CH═CH—CH₃ —OC₅H₁₁ —H —F (457)—C₂H₄—CH═CH₂ —C₃H₇ —H —F (458) —C₂H₄—CH═CH₂ —C₄H₉ —H —F (459)—C₂H₄—CH═CH₂ —C₅H₁₁ —H —F (460) —C₂H₄—CH═CH₂ —CH═CH₂ —H —F (461)—C₂H₄—CH═CH₂ —CH═CH—CH₃ —H —F (462) —C₂H₄—CH═CH₂ —CH₂—CH═CH—CH₃ —H —F(463) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —H —F (464) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH—CH₃—H —F (465) —C₂H₄—CH═CH₂ —OC₂H₅ —H —F (466) —C₂H₄—CH═CH₂ —OC₃H₇ —H —F(467) —C₂H₄—CH═CH₂ —OC₄H₉ —H —F (468) —C₂H₄—CH═CH₂ —OC₅H₁₁ —H —F (469)—C₂H₄—CH═CH—CH₃ —C₃H₇ —H —F (470) —C₂H₄—CH═CH—CH₃ —C₄H₉ —H —F (471)—C₂H₄—CH═CH—CH₃ —C₅H₁₁ —H —F (472) —C₂H₄—CH═CH—CH₃ —CH═CH₂ —H —F (473)—C₂H₄—CH═CH—CH₃ —CH═CH—CH₃ —H —F (474) —C₂H₄—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H—F (475) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH₂ —H —F (476) —C₂H₄—CH═CH—CH₃—C₂H₄—CH═CH—CH₃ —H —F (477) —C₂H₄—CH═CH—CH₃ —OC₂H₅ —H —F (478)—C₂H₄—CH═CH—CH₃ —OC₃H₇ —H —F (479) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —H —F (480)—C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —H —F (481) —OC₂H₅ —C₃H₇ —H —F (482) —OC₂H₅—C₄H₉ —H —F (483) —OC₂H₅ —C₅H₁₁ —H —F (484) —OC₂H₅ —OC₂H₅ —H —F (485)—OC₂H₅ —OC₃H₇ —H —F (486) —OC₂H₅ —OC₄H₉ —H —F (487) —OC₂H₅ —OC₅H₁₁ —H —F(488) —OC₃H₇ —C₃H₇ —H —F (489) —OC₃H₇ —C₄H₉ —H —F (490) —OC₃H₇ —C₅H₁₁ —H—F (491) —OC₃H₇ —OC₂H₅ —H —F (492) —OC₃H₇ —OC₃H₇ —H —F (493) —OC₃H₇—OC₄H₉ —H —F (494) —OC₃H₇ —OC₅H₁₁ —H —F (495) —OC₄H₉ —C₃H₇ —H —F (496)—OC₄H₉ —C₄H₉ —H —F (497) —OC₄H₉ —C₅H₁₁ —H —F (498) —OC₄H₉ —OC₂H₅ —H —F(499) —OC₄H₉ —OC₃H₇ —H —F (500) —OC₄H₉ —OC₄H₉ —H —F (501) —OC₄H₉ —OC₅H₁₁—H —F (502) —OC₅H₁₁ —C₃H₇ —H —F (503) —OC₅H₁₁ —C₄H₉ —H —F (504) —OC₅H₁₁—C₅H₁₁ —H —F (505) —OC₅H₁₁ —OC₂H₅ —H —F (506) —OC₅H₁₁ —OC₃H₇ —H —F (507)—OC₅H₁₁ —OC₄H₉ —H —F (508) —OC₅H₁₁ —OC₅H₁₁ —H —F (509) —C₃H₇ —C₃H₇ —H—CF₃ (510) —C₃H₇ —C₄H₉ —H —CF₃ (511) —C₃H₇ —C₅H₁₁ —H —CF₃ (512) —C₃H₇—OC₂H₅ —H —CF₃ (513) —C₃H₇ —OC₃H₇ —H —CF₃ (514) —C₃H₇ —OC₄H₉ —H —CF₃(515) —C₃H₇ —OC₅H₁₁ —H —CF₃ (516) —C₄H₉ —C₃H₇ —H —CF₃ (517) —C₄H₉ —C₄H₉—H —CF₃ (518) —C₄H₉ —C₅H₁₁ —H —CF₃ (519) —C₄H₉ —OC₂H₅ —H —CF₃ (520)—C₄H₉ —OC₃H₇ —H —CF₃ (521) —C₄H₉ —OC₄H₉ —H —CF₃ (522) —C₄H₉ —OC₅H₁₁ —H—CF₃ (523) —C₅H₁₁ —C₃H₇ —H —CF₃ (524) —C₅H₁₁ —C₄H₉ —H —CF₃ (525) —C₅H₁₁—C₅H₁₁ —H —CF₃ (526) —C₅H₁₁ —OC₂H₅ —H —CF₃ (527) —C₅H₁₁ —OC₃H₇ —H —CF₃(528) —C₅H₁₁ —OC₄H₉ —H —CF₃ (529) —C₅H₁₁ —OC₅H₁₁ —H —CF₃ (530) —OC₂H₅—C₃H₇ —H —CF₃ (531) —OC₂H₅ —C₄H₉ —H —CF₃ (532) —OC₂H₅ —C₅H₁₁ —H —CF₃(533) —OC₂H₅ —OC₂H₅ —H —CF₃ (534) —OC₂H₅ —OC₃H₇ —H —CF₃ (535) —OC₂H₅—OC₄H₉ —H —CF₃ (536) —OC₂H₅ —OC₅H₁₁ —H —CF₃ (537) —OC₃H₇ —C₃H₇ —H —CF₃(538) —OC₃H₇ —C₄H₉ —H —CF₃ (539) —OC₃H₇ —C₅H₁₁ —H —CF₃ (540) —OC₃H₇—OC₂H₅ —H —CF₃ (541) —OC₃H₇ —OC₃H₇ —H —CF₃ (542) —OC₃H₇ —OC₄H₉ —H —CF₃(543) —OC₃H₇ —OC₅H₁₁ —H —CF₃ (544) —OC₄H₉ —C₃H₇ —H —CF₃ (545) —OC₄H₉—C₄H₉ —H —CF₃ (546) —OC₄H₉ —C₅H₁₁ —H —CF₃ (547) —OC₄H₉ —OC₂H₅ —H —CF₃(548) —OC₄H₉ —OC₃H₇ —H —CF₃ (549) —OC₄H₉ —OC₄H₉ —H —CF₃ (550) —OC₄H₉—OC₅H₁₁ —H —CF₃ (551) —OC₅H₁₁ —C₃H₇ —H —CF₃ (552) —OC₅H₁₁ —C₄H₉ —H —CF₃(553) —OC₅H₁₁ —C₅H₁₁ —H —CF₃ (554) —OC₅H₁₁ —OC₂H₅ —H —CF₃ (555) —OC₅H₁₁—OC₃H₇ —H —CF₃ (556) —OC₅H₁₁ —OC₄H₉ —H —CF₃ (557) —OC₅H₁₁ —OC₅H₁₁ —H—CF₃ (558) —C₃H₇ —C₃H₇ —F —CF₃ (559) —C₃H₇ —C₄H₉ —F —CF₃ (560) —C₃H₇—C₅H₁₁ —F —CF₃ (561) —C₃H₇ —OC₂H₅ —F —CF₃ (562) —C₃H₇ —OC₃H₇ —F —CF₃(563) —C₃H₇ —OC₄H₉ —F —CF₃ (564) —C₃H₇ —OC₅H₁₁ —F —CF₃ (565) —C₄H₉ —C₃H₇—F —CF₃ (566) —C₄H₉ —C₄H₉ —F —CF₃ (567) —C₄H₉ —C₅H₁₁ —F —CF₃ (568) —C₄H₉—OC₂H₅ —F —CF₃ (569) —C₄H₉ —OC₃H₇ —F —CF₃ (570) —C₄H₉ —OC₄H₉ —F —CF₃(571) —C₄H₉ —OC₅H₁₁ —F —CF₃ (572) —C₅H₁₁ —C₃H₇ —F —CF₃ (573) —C₅H₁₁—C₄H₉ —F —CF₃ (574) —C₅H₁₁ —C₅H₁₁ —F —CF₃ (575) —C₅H₁₁ —OC₂H₅ —F —CF₃(576) —C₅H₁₁ —OC₃H₇ —F —CF₃ (577) —C₅H₁₁ —OC₄H₉ —F —CF₃ (578) —C₅H₁₁—OC₅H₁₁ —F —CF₃ (579) —CH═CH₂ —C₃H₇ —F —CF₃ (580) —CH═CH₂ —C₄H₉ —F —CF₃(581) —CH═CH₂ —C₅H₁₁ —F —CF₃ (582) —CH═CH₂ —CH═CH₂ —F —CF₃ (583) —CH═CH₂—CH═CH—CH₃ —F —CF₃ (584) —CH═CH₂ —CH₂—CH═CH—CH₃ —F —CF₃ (585) —CH═CH₂—C₂H₄—CH═CH₂ —F —CF₃ (586) —CH═CH₂ —C₂H₄—CH═CH—CH₃ —F —CF₃ (587) —CH═CH₂—OC₂H₅ —F —CF₃ (588) —CH═CH₂ —OC₃H₇ —F —CF₃ (589) —CH═CH₂ —OC₄H₉ —F —CF₃(590) —CH═CH₂ —OC₅H₁₁ —F —CF₃ (591) —CH═CH—CH₃ —C₃H₇ —F —CF₃ (592)—CH═CH—CH₃ —C₄H₉ —F —CF₃ (593) —CH═CH—CH₃ —C₅H₁₁ —F —CF₃ (594)—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (595) —CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃ (596)—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —CF₃ (597) —CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —CF₃(598) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —CF₃ (599) —CH═CH—CH₃ —OC₂H₅ —F —CF₃(600) —CH═CH—CH₃ —OC₃H₇ —F —CF₃ (601) —CH═CH—CH₃ —OC₄H₉ —F —CF₃ (602)—CH═CH—CH₃ —OC₅H₁₁ —F —CF₃ (603) —CH₂—CH═CH—CH₃ —C₃H₇ —F —CF₃ (604)—CH₂—CH═CH—CH₃ —C₄H₉ —F —CF₃ (605) —CH₂—CH═CH—CH₃ —C₅H₁₁ —F —CF₃ (606)—CH₂—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (607) —CH₂—CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃(608) —CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —CF₃ (609) —CH₂—CH═CH—CH₃—C₂H₄—CH═CH₂ —F —CF₃ (610) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —CF₃ (611)—CH₂—CH═CH—CH₃ —OC₂H₅ —F —CF₃ (612) —CH₂—CH═CH—CH₃ —OC₃H₇ —F —CF₃ (613)—CH₂—CH═CH—CH₃ —OC₄H₉ —F —CF₃ (614) —CH₂—CH═CH—CH₃ —OC₅H₁₁ —F —CF₃ (615)—C₂H₄—CH═CH₂ —C₃H₇ —F —CF₃ (616) —C₂H₄—CH═CH₂ —C₄H₉ —F —CF₃ (617)—C₂H₄—CH═CH₂ —C₅H₁₁ —F —CF₃ (618) —C₂H₄—CH═CH₂ —CH═CH₂ —F —CF₃ (619)—C₂H₄—CH═CH₂ —CH═CH—CH₃ —F —CF₃ (620) —C₂H₄—CH═CH₂ —CH₂—CH═CH—CH₃ —F—CF₃ (621) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —F —CF₃ (622) —C₂H₄—CH═CH₂—C₂H₄—CH═CH—CH₃ —F —CF₃ (623) —C₂H₄—CH═CH₂ —OC₂H₅ —F —CF₃ (624)—C₂H₄—CH═CH₂ —OC₃H₇ —F —CF₃ (625) —C₂H₄—CH═CH₂ —OC₄H₉ —F —CF₃ (626)—C₂H₄—CH═CH₂ —OC₅H₁₁ —F —CF₃ (627) —C₂H₄—CH═CH—CH₃ —C₃H₇ —F —CF₃ (628)—C₂H₄—CH═CH—CH₃ —C₄H₉ —F —CF₃ (629) —C₂H₄—CH═CH—CH₃ —C₅H₁₁ —F —CF₃ (630)—C₂H₄—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (631) —C₂H₄—CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃(632) —C₂H₄—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —CF₃ (633) —C₂H₄—CH═CH—CH₃—C₂H₄—CH═CH₂ —F —CF₃ (634) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —CF₃ (635)—C₂H₄—CH═CH—CH₃ —OC₂H₅ —F —CF₃ (636) —C₂H₄—CH═CH—CH₃ —OC₃H₇ —F —CF₃(637) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —F —CF₃ (638) —C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —F—CF₃ (639) —OC₂H₅ —C₃H₇ —F —CF₃ (640) —OC₂H₅ —C₄H₉ —F —CF₃ (641) —OC₂H₅—C₅H₁₁ —F —CF₃ (642) —OC₂H₅ —OC₂H₅ —F —CF₃ (643) —OC₂H₅ —OC₃H₇ —F —CF₃(644) —OC₂H₅ —OC₄H₉ —F —CF₃ (645) —OC₂H₅ —OC₅H₁₁ —F —CF₃ (646) —OC₃H₇—C₃H₇ —F —CF₃ (647) —OC₃H₇ —C₄H₉ —F —CF₃ (648) —OC₃H₇ —C₅H₁₁ —F —CF₃(649) —OC₃H₇ —OC₂H₅ —F —CF₃ (650) —OC₃H₇ —OC₃H₇ —F —CF₃ (651) —OC₃H₇—OC₄H₉ —F —CF₃ (652) —OC₃H₇ —OC₅H₁₁ —F —CF₃ (653) —OC₄H₉ —C₃H₇ —F —CF₃(654) —OC₄H₉ —C₄H₉ —F —CF₃ (655) —OC₄H₉ —C₅H₁₁ —F —CF₃ (656) —OC₄H₉—OC₂H₅ —F —CF₃ (657) —OC₄H₉ —OC₃H₇ —F —CF₃ (658) —OC₄H₉ —OC₄H₉ —F —CF₃(659) —OC₄H₉ —OC₅H₁₁ —F —CF₃ (660) —OC₅H₁₁ —C₃H₇ —F —CF₃ (661) —OC₅H₁₁—C₄H₉ —F —CF₃ (662) —OC₅H₁₁ —C₅H₁₁ —F —CF₃ (663) —OC₅H₁₁ —OC₂H₅ —F —CF₃(664) —OC₅H₁₁ —OC₃H₇ —F —CF₃ (665) —OC₅H₁₁ —OC₄H₉ —F —CF₃ (666) —OC₅H₁₁—OC₅H₁₁ —F —CF₃ (667) —C₃H₇ —C₃H₇ —F —F (668) —C₃H₇ —C₄H₉ —F —F (669)—C₃H₇ —C₅H₁₁ —F —F (670) —C₃H₇ —OC₂H₅ —F —F (671) —C₃H₇ —OC₃H₇ —F —F(672) —C₃H₇ —OC₄H₉ —F —F (673) —C₃H₇ —OC₅H₁₁ —F —F (674) —C₄H₉ —C₄H₉ —F—F (675) —C₄H₉ —C₅H₁₁ —F —F (676) —C₄H₉ —OC₂H₅ —F —F (677) —C₄H₉ —OC₃H₇—F —F (678) —C₄H₉ —OC₄H₉ —F —F (679) —C₄H₉ —OC₅H₁₁ —F —F (680) —C₅H₁₁—C₅H₁₁ —F —F (681) —C₅H₁₁ —OC₂H₅ —F —F (682) —C₅H₁₁ —OC₃H₇ —F —F (683)—C₅H₁₁ —OC₄H₉ —F —F (684) —C₅H₁₁ —OC₅H₁₁ —F —F (685) —CH═CH₂ —C₃H₇ —F —F(686) —CH═CH₂ —C₄H₉ —F —F (687) —CH═CH₂ —C₅H₁₁ —F —F (688) —CH═CH₂—CH═CH₂ —F —F (689) —CH═CH₂ —CH═CH—CH₃ —F —F (690) —CH═CH₂—CH₂—CH═CH—CH₃ —F —F (691) —CH═CH₂ —C₂H₄—CH═CH₂ —F —F (692) —CH═CH₂—C₂H₄—CH═CH—CH₃ —F —F (693) —CH═CH₂ —OC₂H₅ —F —F (694) —CH═CH₂ —OC₃H₇ —F—F (695) —CH═CH₂ —OC₄H₉ —F —F (696) —CH═CH₂ —OC₅H₁₁ —F —F (697)—CH═CH—CH₃ —C₃H₇ —F —F (698) —CH═CH—CH₃ —C₄H₉ —F —F (699) —CH═CH—CH₃—C₅H₁₁ —F —F (700) —CH═CH—CH₃ —CH═CH—CH₃ —F —F (701) —CH═CH—CH₃—CH₂—CH═CH—CH₃ —F —F (702) —CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —F (703)—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F (704) —CH═CH—CH₃ —OC₂H₅ —F —F (705)—CH═CH—CH₃ —OC₃H₇ —F —F (706) —CH═CH—CH₃ —OC₄H₉ —F —F (707) —CH═CH—CH₃—OC₅H₁₁ —F —F (708) —CH₂—CH═CH—CH₃ —C₃H₇ —F —F (709) —CH₂—CH═CH—CH₃—C₄H₉ —F —F (710) —CH₂—CH═CH—CH₃ —C₅H₁₁ —F —F (711) —CH₂—CH═CH—CH₃—CH₂—CH═CH—CH₃ —F —F (712) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —F (713)—CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F (714) —CH₂—CH═CH—CH₃ —OC₂H₅ —F —F(715) —CH₂—CH═CH—CH₃ —OC₃H₇ —F —F (716) —CH₂—CH═CH—CH₃ —OC₄H₉ —F —F(717) —CH₂—CH═CH—CH₃ —OC₅H₁₁ —F —F (718) —C₂H₄—CH═CH₂ —C₃H₇ —F —F (719)—C₂H₄—CH═CH₂ —C₄H₉ —F —F (720) —C₂H₄—CH═CH₂ —C₅H₁₁ —F —F (721)—C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —F —F (722) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH—CH₃ —F —F(723) —C₂H₄—CH═CH₂ —OC₂H₅ —F —F (724) —C₂H₄—CH═CH₂ —OC₃H₇ —F —F (725)—C₂H₄—CH═CH₂ —OC₄H₉ —F —F (726) —C₂H₄—CH═CH₂ —OC₅H₁₁ —F —F (727)—C₂H₄—CH═CH—CH₃ —C₃H₇ —F —F (728) —C₂H₄—CH═CH—CH₃ —C₄H₉ —F —F (729)—C₂H₄—CH═CH—CH₃ —C₅H₁₁ —F —F (730) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F(731) —C₂H₄—CH═CH—CH₃ —OC₂H₅ —F —F (732) —C₂H₄—CH═CH—CH₃ —OC₃H₇ —F —F(733) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —F —F (734) —C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —F —F(735) —OC₂H₅ —OC₂H₅ —F —F (736) —OC₂H₅ —OC₃H₇ —F —F (737) —OC₂H₅ —OC₄H₉—F —F (738) —OC₂H₅ —OC₅H₁₁ —F —F (739) —OC₃H₇ —OC₃H₇ —F —F (740) —OC₃H₇—OC₄H₉ —F —F (741) —OC₃H₇ —OC₅H₁₁ —F —F (742) —OC₄H₉ —OC₄H₉ —F —F (743)—OC₄H₉ —OC₅H₁₁ —F —F (744) —OC₅H₁₁ —OC₅H₁₁ —F —F (745) —C₃H₇ —C₃H₇ —CF₃—CF₃ (746) —C₃H₇ —C₄H₉ —CF₃ —CF₃ (747) —C₃H₇ —C₅H₁₁ —CF₃ —CF₃ (748)—C₃H₇ —OC₂H₅ —CF₃ —CF₃ (749) —C₃H₇ —OC₃H₇ —CF₃ —CF₃ (750) —C₃H₇ —OC₄H₉—CF₃ —CF₃ (751) —C₃H₇ —OC₅H₁₁ —CF₃ —CF₃ (752) —C₄H₉ —C₄H₉ —CF₃ —CF₃(753) —C₄H₉ —C₅H₁₁ —CF₃ —CF₃ (754) —C₄H₉ —OC₂H₅ —CF₃ —CF₃ (755) —C₄H₉—OC₃H₇ —CF₃ —CF₃ (756) —C₄H₉ —OC₄H₉ —CF₃ —CF₃ (757) —C₄H₉ —OC₅H₁₁ —CF₃—CF₃ (758) —C₅H₁₁ —C₅H₁₁ —CF₃ —CF₃ (759) —C₅H₁₁ —OC₂H₅ —CF₃ —CF₃ (760)—C₅H₁₁ —OC₃H₇ —CF₃ —CF₃ (761) —C₅H₁₁ —OC₄H₉ —CF₃ —CF₃ (762) —C₅H₁₁—OC₅H₁₁ —CF₃ —CF₃ (763) —OC₂H₅ —OC₂H₅ —CF₃ —CF₃ (764) —OC₂H₅ —OC₃H₇ —CF₃—CF₃ (765) —OC₂H₅ —OC₄H₉ —CF₃ —CF₃ (766) —OC₂H₅ —OC₅H₁₁ —CF₃ —CF₃ (767)—OC₃H₇ —OC₃H₇ —CF₃ —CF₃ (768) —OC₃H₇ —OC₄H₉ —CF₃ —CF₃ (769) —OC₃H₇—OC₅H₁₁ —CF₃ —CF₃ (770) —OC₄H₉ —OC₄H₉ —CF₃ —CF₃ (771) —OC₄H₉ —OC₅H₁₁—CF₃ —CF₃ (772) —OC₅H₁₁ —OC₅H₁₁ —CF₃ —CF₃

Fluorene compounds of the following formula

are obtained analogously to Example 3:

R¹ R² L¹ L² (800) —C₃H₇ —C₃H₇ —H —F (801) —C₃H₇ —C₄H₉ —H —F (802) —C₃H₇—C₅H₁₁ —H —F (803) —C₃H₇ —OC₂H₅ —H —F (804) —C₃H₇ —OC₃H₇ —H —F (805)—C₃H₇ —OC₄H₉ —H —F (806) —C₃H₇ —OC₅H₁₁ —H —F (807) —C₄H₉ —C₃H₇ —H —F(808) —C₄H₉ —C₄H₉ —H —F (809) —C₄H₉ —C₅H₁₁ —H —F (810) —C₄H₉ —OC₂H₅ —H—F (811) —C₄H₉ —OC₃H₇ —H —F (812) —C₄H₉ —OC₄H₉ —H —F (813) —C₄H₉ —OC₅H₁₁—H —F (814) —C₅H₁₁ —C₃H₇ —H —F (815) —C₅H₁₁ —C₄H₉ —H —F (816) —C₅H₁₁—C₅H₁₁ —H —F (817) —C₅H₁₁ —OC₂H₅ —H —F (818) —C₅H₁₁ —OC₃H₇ —H —F (819)—C₅H₁₁ —OC₄H₉ —H —F (820) —C₅H₁₁ —OC₅H₁₁ —H —F (821) —CH═CH₂ —C₃H₇ —H —F(822) —CH═CH₂ —C₄H₉ —H —F (823) —CH═CH₂ —C₅H₁₁ —H —F (824) —CH═CH₂—CH═CH₂ —H —F (825) —CH═CH₂ —CH═CH—CH₃ —H —F (826) —CH═CH₂—CH₂—CH═CH—CH₃ —H —F (827) —CH═CH₂ —C₂H₄—CH═CH₂ —H —F (828) —CH═CH₂—C₂H₄—CH═CH—CH₃ —H —F (829) —CH═CH₂ —OC₂H₅ —H —F (830) —CH═CH₂ —OC₃H₇ —H—F (831) —CH═CH₂ —OC₄H₉ —H —F (832) —CH═CH₂ —OC₅H₁₁ —H —F (833)—CH═CH—CH₃ —C₃H₇ —H —F (834) —CH═CH—CH₃ —C₄H₉ —H —F (835) —CH═CH—CH₃—C₅H₁₁ —H —F (836) —CH═CH—CH₃ —CH═CH₂ —H —F (837) —CH═CH—CH₃ —CH═CH—CH₃—H —F (838) —CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H —F (839) —CH═CH—CH₃—C₂H₄—CH═CH₂ —H —F (840) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —H —F (841)—CH═CH—CH₃ —OC₂H₅ —H —F (842) —CH═CH—CH₃ —OC₃H₇ —H —F (843) —CH═CH—CH₃—OC₄H₉ —H —F (844) —CH═CH—CH₃ —OC₅H₁₁ —H —F (845) —CH₂—CH═CH—CH₃ —C₃H₇—H —F (846) —CH₂—CH═CH—CH₃ —C₄H₉ —H —F (847) —CH₂—CH═CH—CH₃ —C₅H₁₁ —H —F(848) —CH₂—CH═CH—CH₃ —CH═CH₂ —H —F (849) —CH₂—CH═CH—CH₃ —CH═CH—CH₃ —H —F(850) —CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H —F (851) —CH₂—CH═CH—CH₃—C₂H₄—CH═CH₂ —H —F (852) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —H —F (853)—CH₂—CH═CH—CH₃ —OC₂H₅ —H —F (854) —CH₂—CH═CH—CH₃ —OC₃H₇ —H —F (855)—CH₂—CH═CH—CH₃ —OC₄H₉ —H —F (856) —CH₂—CH═CH—CH₃ —OC₅H₁₁ —H —F (857)—C₂H₄—CH═CH₂ —C₃H₇ —H —F (858) —C₂H₄—CH═CH₂ —C₄H₉ —H —F (859)—C₂H₄—CH═CH₂ —C₅H₁₁ —H —F (860) —C₂H₄—CH═CH₂ —CH═CH₂ —H —F (861)—C₂H₄—CH═CH₂ —CH═CH—CH₃ —H —F (862) —C₂H₄—CH═CH₂ —CH₂—CH═CH—CH₃ —H —F(863) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —H —F (864) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH—CH₃—H —F (865) —C₂H₄—CH═CH₂ —OC₂H₅ —H —F (866) —C₂H₄—CH═CH₂ —OC₃H₇ —H —F(867) —C₂H₄—CH═CH₂ —OC₄H₉ —H —F (868) —C₂H₄—CH═CH₂ —OC₅H₁₁ —H —F (869)—C₂H₄—CH═CH—CH₃ —C₃H₇ —H —F (870) —C₂H₄—CH═CH—CH₃ —C₄H₉ —H —F (871)—C₂H₄—CH═CH—CH₃ —C₅H₁₁ —H —F (872) —C₂H₄—CH═CH—CH₃ —CH═CH₂ —H —F (873)—C₂H₄—CH═CH—CH₃ —CH═CH—CH₃ —H —F (874) —C₂H₄—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —H—F (875) —C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH₂ —H —F (876) —C₂H₄—CH═CH—CH₃—C₂H₄—CH═CH—CH₃ —H —F (877) —C₂H₄—CH═CH—CH₃ —OC₂H₅ —H —F (878)—C₂H₄—CH═CH—CH₃ —OC₃H₇ —H —F (879) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —H —F (880)—C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —H —F (881) —OC₂H₅ —C₃H₇ —H —F (882) —OC₂H₅—C₄H₉ —H —F (883) —OC₂H₅ —C₅H₁₁ —H —F (884) —OC₂H₅ —OC₂H₅ —H —F (885)—OC₂H₅ —OC₃H₇ —H —F (886) —OC₂H₅ —OC₄H₉ —H —F (887) —OC₂H₅ —OC₅H₁₁ —H —F(888) —OC₃H₇ —C₃H₇ —H —F (889) —OC₃H₇ —C₄H₉ —H —F (890) —OC₃H₇ —C₅H₁₁ —H—F (891) —OC₃H₇ —OC₂H₅ —H —F (892) —OC₃H₇ —OC₃H₇ —H —F (893) —OC₃H₇—OC₄H₉ —H —F (894) —OC₃H₇ —OC₅H₁₁ —H —F (895) —OC₄H₉ —C₃H₇ —H —F (896)—OC₄H₉ —C₄H₉ —H —F (897) —OC₄H₉ —C₅H₁₁ —H —F (898) —OC₄H₉ —OC₂H₅ —H —F(899) —OC₄H₉ —OC₃H₇ —H —F (900) —OC₄H₉ —OC₄H₉ —H —F (901) —OC₄H₉ —OC₅H₁₁—H —F (902) —OC₅H₁₁ —C₃H₇ —H —F (903) —OC₅H₁₁ —C₄H₉ —H —F (904) —OC₅H₁₁—C₅H₁₁ —H —F (905) —OC₅H₁₁ —OC₂H₅ —H —F (906) —OC₅H₁₁ —OC₃H₇ —H —F (907)—OC₅H₁₁ —OC₄H₉ —H —F (908) —OC₅H₁₁ —OC₅H₁₁ —H —F (909) —C₃H₇ —C₃H₇ —H—CF₃ (910) —C₃H₇ —C₄H₉ —H —CF₃ (911) —C₃H₇ —C₅H₁₁ —H —CF₃ (912) —C₃H₇—OC₂H₅ —H —CF₃ (913) —C₃H₇ —OC₃H₇ —H —CF₃ (914) —C₃H₇ —OC₄H₉ —H —CF₃(915) —C₃H₇ —OC₅H₁₁ —H —CF₃ (916) —C₄H₉ —C₃H₇ —H —CF₃ (917) —C₄H₉ —C₄H₉—H —CF₃ (918) —C₄H₉ —C₅H₁₁ —H —CF₃ (919) —C₄H₉ —OC₂H₅ —H —CF₃ (920)—C₄H₉ —OC₃H₇ —H —CF₃ (921) —C₄H₉ —OC₄H₉ —H —CF₃ (922) —C₄H₉ —OC₅H₁₁ —H—CF₃ (923) —C₅H₁₁ —C₃H₇ —H —CF₃ (924) —C₅H₁₁ —C₄H₉ —H —CF₃ (925) —C₅H₁₁—C₅H₁₁ —H —CF₃ (926) —C₅H₁₁ —OC₂H₅ —H —CF₃ (927) —C₅H₁₁ —OC₃H₇ —H —CF₃(928) —C₅H₁₁ —OC₄H₉ —H —CF₃ (929) —C₅H₁₁ —OC₅H₁₁ —H —CF₃ (930) —OC₂H₅—C₃H₇ —H —CF₃ (931) —OC₂H₅ —C₄H₉ —H —CF₃ (932) —OC₂H₅ —C₅H₁₁ —H —CF₃(933) —OC₂H₅ —OC₂H₅ —H —CF₃ (934) —OC₂H₅ —OC₃H₇ —H —CF₃ (935) —OC₂H₅—OC₄H₉ —H —CF₃ (936) —OC₂H₅ —OC₅H₁₁ —H —CF₃ (937) —OC₃H₇ —C₃H₇ —H —CF₃(938) —OC₃H₇ —C₄H₉ —H —CF₃ (939) —OC₃H₇ —C₅H₁₁ —H —CF₃ (940) —OC₃H₇—OC₂H₅ —H —CF₃ (941) —OC₃H₇ —OC₃H₇ —H —CF₃ (942) —OC₃H₇ —OC₄H₉ —H —CF₃(943) —OC₃H₇ —OC₅H₁₁ —H —CF₃ (944) —OC₄H₉ —C₃H₇ —H —CF₃ (945) —OC₄H₉—C₄H₉ —H —CF₃ (946) —OC₄H₉ —C₅H₁₁ —H —CF₃ (947) —OC₄H₉ —OC₂H₅ —H —CF₃(948) —OC₄H₉ —OC₃H₇ —H —CF₃ (949) —OC₄H₉ —OC₄H₉ —H —CF₃ (950) —OC₄H₉—OC₅H₁₁ —H —CF₃ (951) —OC₅H₁₁ —C₃H₇ —H —CF₃ (952) —OC₅H₁₁ —C₄H₉ —H —CF₃(953) —OC₅H₁₁ —C₅H₁₁ —H —CF₃ (954) —OC₅H₁₁ —OC₂H₅ —H —CF₃ (955) —OC₅H₁₁—OC₃H₇ —H —CF₃ (956) —OC₅H₁₁ —OC₄H₉ —H —CF₃ (957) —OC₅H₁₁ —OC₅H₁₁ —H—CF₃ (958) —C₃H₇ —C₃H₇ —F —CF₃ (959) —C₃H₇ —C₄H₉ —F —CF₃ (960) —C₃H₇—C₅H₁₁ —F —CF₃ (961) —C₃H₇ —OC₂H₅ —F —CF₃ (962) —C₃H₇ —OC₃H₇ —F —CF₃(963) —C₃H₇ —OC₄H₉ —F —CF₃ (964) —C₃H₇ —OC₅H₁₁ —F —CF₃ (965) —C₄H₉ —C₃H₇—F —CF₃ (966) —C₄H₉ —C₄H₉ —F —CF₃ (967) —C₄H₉ —C₅H₁₁ —F —CF₃ (968) —C₄H₉—OC₂H₅ —F —CF₃ (969) —C₄H₉ —OC₃H₇ —F —CF₃ (970) —C₄H₉ —OC₄H₉ —F —CF₃(971) —C₄H₉ —OC₅H₁₁ —F —CF₃ (972) —C₅H₁₁ —C₃H₇ —F —CF₃ (973) —C₅H₁₁—C₄H₉ —F —CF₃ (974) —C₅H₁₁ —C₅H₁₁ —F —CF₃ (975) —C₅H₁₁ —OC₂H₅ —F —CF₃(976) —C₅H₁₁ —OC₃H₇ —F —CF₃ (977) —C₅H₁₁ —OC₄H₉ —F —CF₃ (978) —C₅H₁₁—OC₅H₁₁ —F —CF₃ (979) —CH═CH₂ —C₃H₇ —F —CF₃ (980) —CH═CH₂ —C₄H₉ —F —CF₃(981) —CH═CH₂ —C₅H₁₁ —F —CF₃ (982) —CH═CH₂ —CH═CH₂ —F —CF₃ (983) —CH═CH₂—CH═CH—CH₃ —F —CF₃ (984) —CH═CH₂ —CH₂—CH═CH—CH₃ —F —CF₃ (985) —CH═CH₂—C₂H₄—CH═CH₂ —F —CF₃ (986) —CH═CH₂ —C₂H₄—CH═CH—CH₃ —F —CF₃ (987) —CH═CH₂—OC₂H₅ —F —CF₃ (988) —CH═CH₂ —OC₃H₇ —F —CF₃ (989) —CH═CH₂ —OC₄H₉ —F —CF₃(990) —CH═CH₂ —OC₅H₁₁ —F —CF₃ (991) —CH═CH—CH₃ —C₃H₇ —F —CF₃ (992)—CH═CH—CH₃ —C₄H₉ —F —CF₃ (993) —CH═CH—CH₃ —C₅H₁₁ —F —CF₃ (994)—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (995) —CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃ (996)—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —CF₃ (997) —CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —CF₃(998) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —CF₃ (999) —CH═CH—CH₃ —OC₂H₅ —F —CF₃(1000) —CH═CH—CH₃ —OC₃H₇ —F —CF₃ (1001) —CH═CH—CH₃ —OC₄H₉ —F —CF₃ (1002)—CH═CH—CH₃ —OC₅H₁₁ —F —CF₃ (1003) —CH₂—CH═CH—CH₃ —C₃H₇ —F —CF₃ (1004)—CH₂—CH═CH—CH₃ —C₄H₉ —F —CF₃ (1005) —CH₂—CH═CH—CH₃ —C₅H₁₁ —F —CF₃ (1006)—CH₂—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (1007) —CH₂—CH═CH—CH₃ —CH═CH—CH₃ —F —CF₃(1008) —CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —CF₃ (1009) —CH₂—CH═CH—CH₃—C₂H₄—CH═CH₂ —F —CF₃ (1010) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —CF₃(1011) —CH₂—CH═CH—CH₃ —OC₂H₅ —F —CF₃ (1012) —CH₂—CH═CH—CH₃ —OC₃H₇ —F—CF₃ (1013) —CH₂—CH═CH—CH₃ —OC₄H₉ —F —CF₃ (1014) —CH₂—CH═CH—CH₃ —OC₅H₁₁—F —CF₃ (1015) —C₂H₄—CH═CH₂ —C₃H₇ —F —CF₃ (1016) —C₂H₄—CH═CH₂ —C₄H₉ —F—CF₃ (1017) —C₂H₄—CH═CH₂ —C₅H₁₁ —F —CF₃ (1018) —C₂H₄—CH═CH₂ —CH═CH₂ —F—CF₃ (1019) —C₂H₄—CH═CH₂ —CH═CH—CH₃ —F —CF₃ (1020) —C₂H₄—CH═CH₂—CH₂—CH═CH—CH₃ —F —CF₃ (1021) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —F —CF₃ (1022)—C₂H₄—CH═CH₂ —C₂H₄—CH═CH—CH₃ —F —CF₃ (1023) —C₂H₄—CH═CH₂ —OC₂H₅ —F —CF₃(1024) —C₂H₄—CH═CH₂ —OC₃H₇ —F —CF₃ (1025) —C₂H₄—CH═CH₂ —OC₄H₉ —F —CF₃(1026) —C₂H₄—CH═CH₂ —OC₅H₁₁ —F —CF₃ (1027) —C₂H₄—CH═CH—CH₃ —C₃H₇ —F —CF₃(1028) —C₂H₄—CH═CH—CH₃ —C₄H₉ —F —CF₃ (1029) —C₂H₄—CH═CH—CH₃ —C₅H₁₁ —F—CF₃ (1030) —C₂H₄—CH═CH—CH₃ —CH═CH₂ —F —CF₃ (1031) —C₂H₄—CH═CH—CH₃—CH═CH—CH₃ —F —CF₃ (1032) —C₂H₄—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —CF₃ (1033)—C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —CF₃ (1034) —C₂H₄—CH═CH—CH₃—C₂H₄—CH═CH—CH₃ —F —CF₃ (1035) —C₂H₄—CH═CH—CH₃ —OC₂H₅ —F —CF₃ (1036)—C₂H₄—CH═CH—CH₃ —OC₃H₇ —F —CF₃ (1037) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —F —CF₃(1038) —C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —F —CF₃ (1039) —OC₂H₅ —C₃H₇ —F —CF₃(1040) —OC₂H₅ —C₄H₉ —F —CF₃ (1041) —OC₂H₅ —C₅H₁₁ —F —CF₃ Δε = −7.0; Δn =0.176 (1042) —OC₂H₅ —OC₂H₅ —F —CF₃ (1043) —OC₂H₅ —OC₃H₇ —F —CF₃ (1044)—OC₂H₅ —OC₄H₉ —F —CF₃ (1045) —OC₂H₅ —OC₅H₁₁ —F —CF₃ (1046) —OC₃H₇ —C₃H₇—F —CF₃ (1047) —OC₃H₇ —C₄H₉ —F —CF₃ (1048) —OC₃H₇ —C₅H₁₁ —F —CF₃ (1049)—OC₃H₇ —OC₂H₅ —F —CF₃ (1050) —OC₃H₇ —OC₃H₇ —F —CF₃ (1051) —OC₃H₇ —OC₄H₉—F —CF₃ (1052) —OC₃H₇ —OC₅H₁₁ —F —CF₃ (1053) —OC₄H₉ —C₃H₇ —F —CF₃ (1054)—OC₄H₉ —C₄H₉ —F —CF₃ (1055) —OC₄H₉ —C₅H₁₁ —F —CF₃ (1056) —OC₄H₉ —OC₂H₅—F —CF₃ (1057) —OC₄H₉ —OC₃H₇ —F —CF₃ (1058) —OC₄H₉ —OC₄H₉ —F —CF₃ (1059)—OC₄H₉ —OC₅H₁₁ —F —CF₃ (1060) —OC₅H₁₁ —C₃H₇ —F —CF₃ (1061) —OC₅H₁₁ —C₄H₉—F —CF₃ (1062) —OC₅H₁₁ —C₅H₁₁ —F —CF₃ (1063) —OC₅H₁₁ —OC₂H₅ —F —CF₃(1064) —OC₅H₁₁ —OC₃H₇ —F —CF₃ (1065) —OC₅H₁₁ —OC₄H₉ —F —CF₃ (1066)—OC₅H₁₁ —OC₅H₁₁ —F —CF₃ (1067) —C₃H₇ —C₃H₇ —F —F (1068) —C₃H₇ —C₄H₉ —F—F (1069) —C₃H₇ —C₅H₁₁ —F —F (1070) —C₃H₇ —OC₂H₅ —F —F (1071) —C₃H₇—OC₃H₇ —F —F (1072) —C₃H₇ —OC₄H₉ —F —F (1073) —C₃H₇ —OC₅H₁₁ —F —F (1074)—C₄H₉ —C₄H₉ —F —F (1075) —C₄H₉ —C₅H₁₁ —F —F (1076) —C₄H₉ —OC₂H₅ —F —F(1077) —C₄H₉ —OC₃H₇ —F —F (1078) —C₄H₉ —OC₄H₉ —F —F (1079) —C₄H₉ —OC₅H₁₁—F —F (1080) —C₅H₁₁ —C₅H₁₁ —F —F (1081) —C₅H₁₁ —OC₂H₅ —F —F (1082)—C₅H₁₁ —OC₃H₇ —F —F (1083) —C₅H₁₁ —OC₄H₉ —F —F (1084) —C₅H₁₁ —OC₅H₁₁ —F—F (1085) —CH═CH₂ —C₃H₇ —F —F (1086) —CH═CH₂ —C₄H₉ —F —F (1087) —CH═CH₂—C₅H₁₁ —F —F (1088) —CH═CH₂ —CH═CH₂ —F —F (1089) —CH═CH₂ —CH═CH—CH₃ —F—F (1090) —CH═CH₂ —CH₂—CH═CH—CH₃ —F —F (1091) —CH═CH₂ —C₂H₄—CH═CH₂ —F —F(1092) —CH═CH₂ —C₂H₄—CH═CH—CH₃ —F —F (1093) —CH═CH₂ —OC₂H₅ —F —F (1094)—CH═CH₂ —OC₃H₇ —F —F (1095) —CH═CH₂ —OC₄H₉ —F —F (1096) —CH═CH₂ —OC₅H₁₁—F —F (1097) —CH═CH—CH₃ —C₃H₇ —F —F (1098) —CH═CH—CH₃ —C₄H₉ —F —F (1099)—CH═CH—CH₃ —C₅H₁₁ —F —F (1100) —CH═CH—CH₃ —CH═CH—CH₃ —F —F (1101)—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —F (1102) —CH═CH—CH₃ —C₂H₄—CH═CH₂ —F —F(1103) —CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F (1104) —CH═CH—CH₃ —OC₂H₅ —F —F(1105) —CH═CH—CH₃ —OC₃H₇ —F —F (1106) —CH═CH—CH₃ —OC₄H₉ —F —F (1107)—CH═CH—CH₃ —OC₅H₁₁ —F —F (1108) —CH₂—CH═CH—CH₃ —C₃H₇ —F —F (1109)—CH₂—CH═CH—CH₃ —C₄H₉ —F —F (1110) —CH₂—CH═CH—CH₃ —C₅H₁₁ —F —F (1111)—CH₂—CH═CH—CH₃ —CH₂—CH═CH—CH₃ —F —F (1112) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH₂—F —F (1113) —CH₂—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F (1114) —CH₂—CH═CH—CH₃—OC₂H₅ —F —F (1115) —CH₂—CH═CH—CH₃ —OC₃H₇ —F —F (1116) —CH₂—CH═CH—CH₃—OC₄H₉ —F —F (1117) —CH₂—CH═CH—CH₃ —OC₅H₁₁ —F —F (1118) —C₂H₄—CH═CH₂—C₃H₇ —F —F (1119) —C₂H₄—CH═CH₂ —C₄H₉ —F —F (1120) —C₂H₄—CH═CH₂ —C₅H₁₁—F —F (1121) —C₂H₄—CH═CH₂ —C₂H₄—CH═CH₂ —F —F (1122) —C₂H₄—CH═CH₂—C₂H₄—CH═CH—CH₃ —F —F (1123) —C₂H₄—CH═CH₂ —OC₂H₅ —F —F (1124)—C₂H₄—CH═CH₂ —OC₃H₇ —F —F (1125) —C₂H₄—CH═CH₂ —OC₄H₉ —F —F (1126)—C₂H₄—CH═CH₂ —OC₅H₁₁ —F —F (1127) —C₂H₄—CH═CH—CH₃ —C₃H₇ —F —F (1128)—C₂H₄—CH═CH—CH₃ —C₄H₉ —F —F (1129) —C₂H₄—CH═CH—CH₃ —C₅H₁₁ —F —F (1130)—C₂H₄—CH═CH—CH₃ —C₂H₄—CH═CH—CH₃ —F —F (1131) —C₂H₄—CH═CH—CH₃ —OC₂H₅ —F—F (1132) —C₂H₄—CH═CH—CH₃ —OC₃H₇ —F —F (1133) —C₂H₄—CH═CH—CH₃ —OC₄H₉ —F—F (1134) —C₂H₄—CH═CH—CH₃ —OC₅H₁₁ —F —F (1135) —OC₂H₅ —OC₂H₅ —F —F(1136) —OC₂H₅ —OC₃H₇ —F —F (1137) —OC₂H₅ —OC₄H₉ —F —F (1138) —OC₂H₅—OC₅H₁₁ —F —F (1139) —OC₃H₇ —OC₃H₇ —F —F (1140) —OC₃H₇ —OC₄H₉ —F —F(1141) —OC₃H₇ —OC₅H₁₁ —F —F (1142) —OC₄H₉ —OC₄H₉ —F —F (1143) —OC₄H₉—OC₅H₁₁ —F —F (1144) —OC₅H₁₁ —OC₅H₁₁ —F —F (1145) —C₃H₇ —C₃H₇ —CF₃ —CF₃(1146) —C₃H₇ —C₄H₉ —CF₃ —CF₃ (1147) —C₃H₇ —C₅H₁₁ —CF₃ —CF₃ (1148) —C₃H₇—OC₂H₅ —CF₃ —CF₃ (1149) —C₃H₇ —OC₃H₇ —CF₃ —CF₃ (1150) —C₃H₇ —OC₄H₉ —CF₃—CF₃ (1151) —C₃H₇ —OC₅H₁₁ —CF₃ —CF₃ (1152) —C₄H₉ —C₄H₉ —CF₃ —CF₃ (1153)—C₄H₉ —C₅H₁₁ —CF₃ —CF₃ (1154) —C₄H₉ —OC₂H₅ —CF₃ —CF₃ (1155) —C₄H₉ —OC₃H₇—CF₃ —CF₃ (1156) —C₄H₉ —OC₄H₉ —CF₃ —CF₃ (1157) —C₄H₉ —OC₅H₁₁ —CF₃ —CF₃(1158) —C₅H₁₁ —C₅H₁₁ —CF₃ —CF₃ (1159) —C₅H₁₁ —OC₂H₅ —CF₃ —CF₃ (1160)—C₅H₁₁ —OC₃H₇ —CF₃ —CF₃ (1161) —C₅H₁₁ —OC₄H₉ —CF₃ —CF₃ (1162) —C₅H₁₁—OC₅H₁₁ —CF₃ —CF₃ (1163) —OC₂H₅ —OC₂H₅ —CF₃ —CF₃ (1164) —OC₂H₅ —OC₃H₇—CF₃ —CF₃ (1165) —OC₂H₅ —OC₄H₉ —CF₃ —CF₃ (1166) —OC₂H₅ —OC₅H₁₁ —CF₃ —CF₃(1167) —OC₃H₇ —OC₃H₇ —CF₃ —CF₃ (1168) —OC₃H₇ —OC₄H₉ —CF₃ —CF₃ (1169)—OC₃H₇ —OC₅H₁₁ —CF₃ —CF₃ (1170) —OC₄H₉ —OC₄H₉ —CF₃ —CF₃ (1171) —OC₄H₉—OC₅H₁₁ —CF₃ —CF₃ (1172) —OC₅H₁₁ —OC₅H₁₁ —CF₃ —CF₃

1. A fluorene compound of formula IR¹—(—A¹—Z¹—)_(k1)—(—A²—Z²—)_(k2)—W—(—Z³—A³—)_(k3)—(—Z⁴—A⁴—)_(k4)—R²  Iin which W is the

 group, L¹ and L², independently of one another, are H, F, Cl, —CH₂F,—CHF₂ or —CF₃, with the proviso that L¹ and L² are not both H, L³ andL⁴, independently of one another, are H or F, wherein one of L³ and L⁴is H and the other is F, R¹ and R², independently of one another, are H,halogen, —CN, —NCS, —SF₅ or alkyl having from 1 to 18 carbon atoms, inwhich, in addition, one or two non-adjacent —CH₂— groups may be replacedby —O—, —S—, —CO—, —O—CO—, —CO—O—, —E— and/or —C≡C—and/or in which, inaddition, one or more H atoms may be replaced by halogen and/or —CN, Eis CR⁴═CR⁵ or CHR⁴—CHR⁵, R⁴ and R⁵ are each, independently of oneanother, H, alkyl having 1–6 carbon atoms, F, Cl, CF₃ or CN, A¹, A², A³and A⁴ are each, independently of one another, 1,4-phenylene, in whichone or more CH groups may be replaced by N, 1,4-cyclohexylene, in whichone or two non-adjacent CH₂ groups may be replaced by O and/or S,1,4-cyclohexenylene, 1,4- bicyclo[2.2.2]octylene, piperidine-1,4-diyl,naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or1,2,3,4-tetrahydronaphthalene-2,6-diyl, where, in the meanings given forA¹, A², A³ and A⁴, one or more H atoms may be substituted by halogen,—CN and/or alkyl having from 1 to 6 carbon atoms, in which one or more Hatoms may be replaced by halogen or —CN, and/or in which one or morenon-adjacent —CH₂— groups may be replaced, independently of one another,by —CO—, —O—CO—, —CO—O—, —O—, —S—, —CH═CH— or —C≡C—, and Z¹, Z², Z³ andZ⁴, independently of one another, are —O—CO—, —CO—O—, —CH₂—O—, —CF₂—O—,—O—CH₂—, —O—CF₂—, —C₂H₄—, —CH₂—CF₂—, —CF₂—CH₂—, —CF₂—CF₂—, —CH═CH—,—CF═CH—, —CH═CF—, —CF═CF—, —C≡C— or a single bond, k1, k2, k3 and k4,independently of one another, are 0, 1 or
 2. 2. A fluorene compoundaccording to claim 1, wherein said compound is of formula IaR¹—W—R²  Ia.
 3. A fluorene compound according to claim 1, wherein saidcompound is of formula IbR¹—A¹—Z¹—W—R²  Ib.
 4. A fluorene compound according to claim 1, whereinsaid compound is of formula Ic or IdR¹—A¹—Z¹—A²—Z²—W—R²  IcR¹—A¹—Z¹—W—Z³—A³—R²  Id.
 5. A fluorene compound according to claim 1,whereinR¹—(—A¹—Z¹—)_(k1)—(—A²—Z²—)_(k2)— and—(—Z³—A³—)_(k3)—(—Z⁴—A⁴—)_(k4)—R² are each selected so that the fluorenecompound has a dielectric anisotropy Δε of less than or equal to −6.0.6. A liquid-crystalline medium having two or more liquid-crystallinecomponents, wherein said medium comprises at least one compoundaccording to claim
 1. 7. In an optical display element containing aliquid-crystalline medium, the improvement wherein said medium is aliquid-crystalline medium according to claim
 6. 8. In an electro-opticaldisplay element containing a liquid-crystalline medium as a dielectric,the improvement wherein said medium is a liquid-crystalline mediumaccording to claim 6.